Program and Abstracts - University of Victoria

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IRIS-13 Victoria

IRIS-13 Schedule of Events at a Glance 

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IRIS-13 Victoria 

Sunday 29 July Monday 30 July Tuesday 31 July Wednesday 1 August Thursday 2 August 

8:30 

Registration Registration Registration Registration 

8:40 Welcome 

8:50 Hsieh Jaekle Piers 8:50 Liu, S-Y Wisian-Neilson 

9:00 Bertrand 9:00 O19/Po65 B O20 P5 A O38 B O39 

9:10 P1 Sasamori Knight Fischer Vargas-Baca 

9:20 A O21 B O22 A O40 B O41 

9:30 Saito, M Rosenberg Reed 9:30 Macdonald Uhlig 

9:40 Bourissou 9:40 A O23 B O24 K7 A O42 B O43 

9:50 K1 West Tokitoh Ruzicka Less 

10:00 A O25 B O26 Weigand 10:00 A O44 B O45 

10:10 Laitinen 10:10 Percival Knapp K8 Neilson Baker 

10:20 K2 A O27 B O28 A O46 B O47 

10:30 Coffee Coffee Coffee 

10:40 Coffee 10:30-10:50 10:30-10:50 10:30-10:50 

10:50 10:40-11:00 Saito, S Rivard Aldridge 10:50 Hayward Moya-Cabrera 

11:00 Dehnen 11:00 A O29 B O30 K9 A O48 B O49 

11:10 K3 Liu, C-W Price Boere Jancik 

11:20 A O31 B O32 Frenking 11:20 A O50 B O51 

11:30 Sekiguchi 11:30 Mori Passmore K10 Masuda Jurkschat 

11:40 P2 A O33 B O34 A O52 B O53 

11:50 Tacke Dielmann Hey-Hawkins 11:50 Roesler Hasken 

12:00 A O35 B O36 P6 A O54 B O55 

12:10 Lunch 12:10-1:40 Lunch 12:10-1:40 Lunch 12:10-1:40 

12:20 Delta Hotel Delta Hotel Delta Hotel 

12:30 Harbour Room Harbour Room Free Time Harbour Room 

1:40 Beckmann Omae Braunschweig 1:40 

Jones 1:40 

1:50 A O1 B O2 P3 P7 

2:00 Scheer Gross 

2:10 A O3 B O4 

2:20 Rautianen Schulz Cummins 2:20 Ragogna 2:20 

2:30 A O5 B O6 K4 K11 

2:40 Preuss Gudat 

2:50 A O7 B O8 Baines 2:50 Gabbai 2:50 

3:00 Registration Wahler Chivers K5 K12 

3:10 Delta Hotel A O9 B O10 

3:20 Foyer Coffee Coffee Coffee 

3:30 3:20-3:40 3:20-3:40 3:20-3:40 

3:40 von Haenisch Townsend Scheschkewitz 3:40 Wright 3:40 

3:50 A O11 B O12 K6 K13 

4:00 Streubel Leitao 

4:10 A O13 B O14 Power 4:10 Driess 4:10 

4:20 Chakrahari Wolf P4 P8 

4:30 A O15 B O16 

4:40 Wazir Baumgartner 

4:50 A O17 B O18 Schnepf 4:50 Closing Remarks 

5:00 Poster Reception A O37 Reception 5:00 

5:10 5:00-7:30 Poster Reception B 

6:30 Mixer, Museum Delta Hotel 5:10-7:30 Banquet, Delta Hotel 

6:30-9:30 

Delta Hotel 6:30-9:30

IRIS-13 

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13 th International Symposium on Inorganic Ring Systems 

29 July – 2 August 2012 

at 

Delta Victoria Ocean Pointe Resort, 45 Songhees Road, Victoria, British Columbia 

V9A 6T3, Canada 

http://web.uvic.ca/~iris13 

Program and Abstracts 

IRIS occurs every three years and is the premier international showcase for Main Group Chemistry, 

including Organometallic Chemistry and Inorganic Materials Chemistry. The IRIS meetings bring 

together leading professors, postdoctoral fellows and research students from around the world. 

The History of IRIS 

Year Town Country Host/Chair 

IRIS-1 1975 Besancon France H. Garcia-Fernandez 

IRIS-1b 1977 Madrid Spain H. Garcia-Fernandez 

IRIS-2 1978 Göttingen Germany O. Glemser 

IRIS-3 1981 Graz Austria E. Hengge 

IRIS-4 1985 Paris France H. Garcia-Fernandez 

IRIS-5 1988 Amherst Massachusetts, USA R. R. Holmes 

IRIS-6 1991 Berlin Germany R. Steudel 

IRIS-7 1994 Banff Alberta, Canada T. Chivers 

IRIS-8 1997 Loughborough UK J. D. Woollins 

IRIS-9 2000 Saarbrücken Germany M. Veith 

IRIS-10 2003 Burlington Vermont, USA C. Allen 

IRIS-11 2006 Oulu Finland R. S. Laitinen 

IRIS-12 2009 Goa India P. Mathur

Welcome 

4 


Welcome to the 13th International Symposium on Inorganic Ring Systems and welcome to Victoria, BC. 

UVic is honoured to be hosting and sponsoring the premier international forum for Main Group 

Chemistry. The IRIS-13 conference provides an excellent opportunity to foster national and international 

collaboration in this important research field. Chemistry plays a fundamental role in many of UVic’s 

research strengths, across a number of disciplines. Our highly successful and internationally-recognised 

faculty and students in the UVic Department of Chemistry are excited to be given the opportunity at IRIS- 

13 to showcase their work and build on their mission of fostering world-class research and outstanding 

chemical education. I hope you have a wonderful time with us in Victoria. 

Dr. Howard Brunt 

Vice-President Research 

University of Victoria 

Welcome to IRIS-13 and beautiful Victoria. We are delighted to present an outstanding scientific program 

that will be augmented by the picturesque setting of the inner harbour and the Olympic mountains. The 

program begins with a mixer on Sunday evening at the Royal BC Museum, offering a fascinating 

experience of native art and displays with an array of culinary delights. The scientific oral presentations 

are scheduled for Monday, Tuesday, Wednesday morning and Thursday, with poster sessions on Monday 

and Tuesday evening. I am grateful for the excellent advice and support of my colleagues on the 

International Advisory Board, the National Advisory Committee and the Local Organizing Committee 

during the development of this exciting program. 

We are grateful to the Delta Victoria Ocean Pointe Resort and Spa, our host for IRIS-13, for their 

partnership in the organization of IRIS-13. The Delta will serve a buffet lunch for all registrants on 

Monday, Tuesday and Thursday, and will host the symposium banquet on Thursday evening. 

Wednesday lunchtime and afternoon are designated as free time to give you an opportunity for outdoor 

activities including golf, hiking, sailing, fishing, sight seeing and whale watching. Alternatively, the 

downtown offers numerous sightseeing options within walking distance, and a wide selection of shops, 

restaurants and bars. 

We are especially grateful for the financial support of the sponsors who have made this event possible. 

Enjoy, 

N 

Neil Burford 

Symposium Chair 

Chair, Department of Chemistry 

University of Victoria

Message from Rob Lipson, Dean of Science, University of Victoria 

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On behalf of the Faculty of Science of the University of Victoria I am delighted to welcome you to the 

13th International Symposium on Inorganic Ring Systems. The list of plenary and invited speakers is 

truly impressive. In addition to a strong Canadian contingent I note and welcome chemists from many 

other countries including the US, France, Japan, India, the Czech Republic, Finland and Australia. 

The last time an IRIS conference was held in Canada was in 1994. I am particularly pleased that you are 

meeting in Victoria in 2012 because in the last decade UVic has emerged to be a widely acknowledged 

driver of research excellence both nationally and internationally. The Department of Chemistry is one the 

big reasons that UVic is now ranked as one of the top 200 universities in the world. I feel particularly 

qualified to be able to make that assertion not only in my role as Dean, but also as a chemist. 

I wish to congratulate my UVic colleagues Neil Burford, Robin Hicks, Scott McIndoe, and Lisa 

Rosenberg, as well as Derek Gates from UBC, for their efforts as members of the Local Organizing 

Committee in putting together such a fine program. 

My understanding is that IRIS takes place every three years. Given the rapid changes that can take place 

within any particular scientific discipline over that time scale, I am confident that the symposium will be 

highly stimulating. I wish all the participants whether they be professors, postdoctoral fellows or research 

students a successful and enjoyable stay. And if you get the chance I invite you visit to our beautiful 

campus. 

Best regards 

Rob Lipson 

PO Box 1700 STN CSC Victoria British 

Columbia V8W 2Y2 Canada Tel (250) 

721-7062, Fax (250) 472-5012 Web 

http://www.uvic.ca/science/ 

Faculty of Science 

Office of the Dean

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The organizers acknowledge the generous support of the following Sponsors: 

Department of Chemistry 



Faculty of Science 

Office of the Vice President Research 

Office of the Vice President Academic and Provost 

MBraun Incorporated USA 

John Wiley & Sons

IRIS International Advisory Board 

C.W. Allen (USA) H.W. Roesky (Germany) 

T. Chivers (Canada) R. Streubel (Germany) 

A.H. Cowley (USA) N. Tokitoh (Japan) 

R.R. Holmes (USA) F. Uhlig (Austria) 

R. Laitinen (Finland) M. Veith (Germany) 

J.P. Majoral (France) R. West (USA) 

P. Mathur (India) J.D. Woollins (UK) 

IRIS-13 National Advisory Committee 

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Kim Baines (Western) Tom Baker (Ottawa) 

Thomas Baumgartner (Calgary) René Boeré (Lethbridge) 

Glen Briand (Mount Allison) Tris Chivers (Calgary) 

Jason Clyburne (Saint Mary's) Adam Dyker (New Brunswick) 

Bobby Ellis (Acadia) Chuck Macdonald (Windsor) 

Jason Masuda (Saint Mary's) Jack Passmore (New Brunswick) 

Kathryn Preuss (Guelph) Paul Ragogna (Western) 

Jeremy Rawson (Windsor) Eric Rivard (Alberta) 

Roland Roesler (Calgary) Doug Stephan (Toronto) 

Ignacio Vargas-Baca (McMaster) 

IRIS-13 Local Organizing Committee 

Neil Burford (Victoria), Symposium Chair 

Derek Gates (UBC) 

Robin Hicks (Victoria) 

Scott McIndoe (Victoria) 

Lisa Rosenberg (Victoria)

Registration, Mixer, Lunches and Banquet 

Registration: Sunday 29 July, 3:00-6:30 p.m. 

Monday 30 July, 8:00-8:40 a.m. 

Tuesday 31 July, 8:30-8:50 a.m. 

Wednesday 1 August, 8:30-8:50 a.m. 

Thursday 2 August, 8:30-8:50 a.m. 

at the Delta Victoria Ocean Pointe Resort, Foyer 

Opening Mixer: Sunday 29 July, 6:30-9:30 p.m. 

at the Royal BC Museum 

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Lunch: Monday 30 July, 12:10-1:40 p.m. 

at the Delta Victoria Ocean Pointe Resort, Harbour Room 

Lunch: Tuesday 31 July, 12:10-1:40 p.m. 


Lunch: Thursday 2 August, 12:10-1:40 p.m. 


Reception: Thursday 2 August, 5:00-6:30 p.m. 

at the Delta Victoria Ocean Pointe Resort, Foyer 

Banquet: Thursday 2 August, 6:30-9:30 p.m. 

at the Delta Victoria Ocean Pointe Resort, Ballroom

Monday 30 July 

Plenary, Keynote and Oral Contributions 

in the Ballroom 

9:00 a.m. – 12:10 p.m. (coffee at 10:40 a.m.) 

Session Chair: Robin Hicks, University of Victoria 

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Plenary 1: Guy Bertrand, UCR/CNRS, University of California, Riverside, USA (9:00 a.m.) 

Keynote 1: Didier Bourissou, Université Paul Sabatier, France (9:40 a.m.) 

Keynote 2: Risto Laitinen, University of Oulu, Finland (10:10 a.m.) 

Keynote 3: Stefanie Dehnen, Philipps-Universität, Marburg, Germany (11:00 a.m.) 

Plenary 2: Akira Sekiguchi, University of Tsukuba, Japan (11:30 a.m.) 

Lunch: at the Delta Victoria Ocean Pointe Resort, Harbour Room (12:10-1:40 p.m.) 

1:40 p.m. – 5:00 p.m. (coffee at 3:20 p.m.) 

Session Chairs: Room A - Charles Macdonald, University of Windsor 

Room B - Lisa Rosenberg, University of Victoria 

Oral 1: Jens Beckmann, Bremen University, Germany (A-1:40 p.m.) 

Oral 2: Iwao Omae, Omae Research Laboratories, Sayama, Saitama, Japan (B-1:40 p.m.) 

Oral 3: Manfred Scheer, University of Regensburg, Germany (A-2:00 p.m.) 

Oral 4: Uwe Gross, Graz University of Technology, Austria (B-2:00 p.m.) 

Oral 5: Mikko Rautiainen, University of Oulu, Finland (A-2:20 p.m.) 

Oral 6: Axel Schulz, University of Rostock, Germany (B-2:20 p.m.) 

Oral 7: Kathryn Preuss, University of Guelph, Canada (A-2:40 p.m.) 

Oral 8: Dietrich Gudat, Universität Stuttgart, Germany (B-2:40 p.m.) 

Oral 9: Johannes Wahler, Julius-Maximilians-University Würzburg, Germany (A-3:00 p.m.) 

Oral 10: Tristram Chivers, University of Calgary, Canada (B-3:00 p.m.) 

Oral 11: Carsten von Hänisch, Philipps-Universität-Marburg, Germany (A-3:40 p.m.) 

Oral 12: Nell Townsend, University of Bristol, UK (B-3:40 p.m.) 

Oral 13: Rainer Streubel, Rheinische Friedrich-Wilhelms Univ. Bonn, Germany (A-4:00 p.m.) 

Oral 14: Erin Leitao, University of Bristol, UK (B-4:00 p.m.) 

Oral 15: Kiran Kumar Varma Chakrahari, IIT Madras, India (A-4:20 p.m.) 

Oral 16: Robert Wolf, University of Regensburg, Germany (B-4:20 p.m.) 

Oral 17: Hameed Ullah Wazir, Hazara University Mansehra, Pakistan (A-4:40 p.m.) 

Oral 18: Thomas Baumgartner, University of Calgary, Canada (B-4:40 p.m.)

Plenary, Keynote and Oral Contributions (continued) 


Tuesday 31 July 


Session Chairs: Room A - Rene Boere, University of Lethbridge 

Room B - Glen Briand, Mount Allison University 

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Oral 19: Tom Hsieh, University of British Columbia, Canada (A-8:50 a.m.) 

Oral 20: Frieder Jäkle, Rutgers University, USA (B-8:50 a.m.) 

Oral 21: Takahiro Sasamori, Kyoto University, Japan (A-9:10 a.m.) 

Oral 22: Fergus Knight, University of St Andrews, UK (B-9:10 a.m.) 

Oral 23: Masaichi Saito, Saitama University, Japan (A-9:30 a.m.) 

Oral 24: Lisa Rosenberg, University of Victoria (B-9:30 a.m.) 

Oral 25: Robert West, University of Wisconsin, USA (A-9:50 a.m.) 

Oral 26: Norihiro Tokitoh, Kyoto University, Japan (B-9:50 a.m.) 

Oral 27: Paul Percival, Simon Fraser University, Canada (A-10:10 a.m.) 

Oral 28: Carsten Knapp, Bergische Universität Wuppertal, Germany (B-10:10 a.m.) 

Oral 29: Shohei Saito, Nagoya University, Japan (A-10:50 a.m.) 

Oral 30: Eric Rivard, University of Alberta, Canada (B-10:50 a.m.) 

Oral 31: Chen-Wei Liu, National Dong Hwa University, Taiwan (A-11:10 a.m.) 

Oral 32: Jacquelyn Price, Western University, Canada (B-11:10 a.m.) 

Oral 33: Takao Mori, National Institute for Materials Science, Tsukuba, Japan (A-11:30 a.m.) 

Oral 34: Jack Passmore, University of New Brunswick, Canada (B-11:30 a.m.) 

Oral 35: Reinhold Tacke, Julius-Maximilians-University Würzburg, Germany (A-11:50 a.m.) 

Oral 36: Fabian Dielmann, University of California, Riverside, USA (B-11:50 a.m.) 


1:40 p.m. – 5:10 p.m. (coffee at 3:20 a.m.) 

Session Chair: Tom Baker, University of Ottawa 

Plenary 3: Holger Braunschweig, University of Würzburg, Germany (1:40 p.m.) 

Keynote 4: Christopher Cummins, Massachusetts Institute of Technology, USA (2:20 p.m.) 

Keynote 5: Kim Baines, Western University, Canada (2:50 p.m.) 

Keynote 6: David Scheschkewitz, Saarland University, Germany (3:40 p.m.) 

Plenary 4: Philip Power, University of California, Davis, USA (4:10 p.m.) 

Oral 37: Andreas Schnepf, University Duisburg-Essen, Germany (4:50 p.m.) 

Wednesday 1 August 


Session Chair: Derek Gates, University of British Columbia 

Plenary 5: Warren Piers, University of Calgary, Canada (8:50 a.m.) 

Keynote 7: Christopher Reed, University of California, Riverside, USA (9:30 a.m.) 

Keynote 8: Jan Weigand, Westfälische Wilhelms-Universität Münster, Germany (10:00 a.m.) 

Keynote 9: Simon Aldridge, University of Oxford, UK (10:50 a.m.) 

Keynote 10: Gernot Frenking, Philipps-Universität, Marburg, Germany (11:20 a.m.) 

Plenary 6: Evamarie Hey-Hawkins, Universität Leipzig, Germany (11:50 a.m.)

Thursday 2 August 

Plenary, Keynote and Oral Contributions (continued) 



Session Chairs: Room A - Thomas Baumgartner, University of Calgary 

Room B - Jason Clyburne, Saint Mary’s University 

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Oral 38: Shih-Yuan Liu, University of Oregon, USA (A-8:50 a.m.) 

Oral 39: Patty Wisian-Neilson, Southern Methodist University, USA (B-8:50 a.m.) 

Oral 40: Roland Fischer, Graz University of Technology, Austria (A-9:10 a.m.) 

Oral 41: Ignacio Vargas-Baca, McMaster University, Canada (B-9:10 a.m.) 

Oral 42: Charles Macdonald, University of Windsor, Canada (A-9:30 a.m.) 

Oral 43: Frank Uhlig, Graz University of Technology, Austria (B-9:30 a.m.) 

Oral 44: Ales Ruzicka, University of Pardubice, Czech Republic (A-9:50 a.m.) 

Oral 45: Robert Less, Cambridge University, UK (B-9:50 a.m.) 

Oral 46: Robert Neilson, Texas Christian University, USA (A-10:10 a.m.) 

Oral 47: Tom Baker, University of Ottawa, Canada (B-10:10 a.m.) 

Oral 48: John Hayward, University of Windsor, Canada (A-10:50 a.m.) 

Oral 49: Monica Moya-Cabrera, Univ. Nacional Autónoma de México, Mexico (B-10:50 a.m.) 

Oral 50: Rene Boeré, University of Lethbridge, Canada (A-11:10 a.m.) 

Oral 51: Vojtech Jancik, Centro Conjunto de Invest. en Química Sust., Mexico (B-11:10 a.m.) 

Oral 52: Jason Masuda, Saint Mary's University, Canada (A-11:30 a.m.) 

Oral 53: Klaus Jurschat, Technische Universität Dortmund, Germany (B-11:30 a.m.) 

Oral 54: Roland Roesler, University of Calgary, Canada (A-11:50 a.m.) 

Oral 55: Bernd Hasken, Graz University of Technology, Austria (B-11:50 a.m.) 


1:40 p.m. – 4:50 p.m. (coffee at 3:20 p.m.) 

Session Chair: Tristram Chivers, University of Calgary 

Plenary 7: Cameron Jones, Monash University, Australia (1:40 p.m.) 

Keynote 11: Paul Ragogna, Western University, Canada (2:20 p.m.) 

Keynote 12: François P. Gabbaï, Texas A&M University, USA (2:50 p.m.) 

Keynote 13: Dominic Wright, Cambridge University, UK (3:40 p.m.) 

Plenary 8: Matthias Driess, Technische Universität Berlin, Germany (4:10 p.m.)

Contributed Poster Presentations 

Poster Session A, Monday 30 July, 5:00 p.m. – 7:30 p.m. 

1. Jason Clyburne, Saint Mary’s University, Canada 

2. Klaus Dück, Julius-Maximilians-University Würzburg, Germany 

3. Thomas Kramer, Julius-Maximilians-University Würzburg, Germany 

4. Katharina Ferkinghoff, Julius-Maximilians-University Würzburg, Germany 

5. Johannes Brand, Julius-Maximilians-University Würzburg, Germany 

6. Rong Shang, Julius-Maximilians-University Würzburg, Germany 

7. Christian Hörl, Julius-Maximilians-University Würzburg, Germany 

8. Ala Swidan, University of Windsor, Canada 

9. Michal Horáček, Institute of Physical Chemistry of Academy of Sciences, Czech Republic 

10. Alexander Villinger, University of Rostock, Germany 

11. Michael Feierabend, Philipps-Universität Marburg, Germany 

12. Christian Bimbös, Philipps-Universität Marburg, Germany 

13. Koh Sugamata, Kyoto University, Japan 

14. Krista Morrow, University of Victoria, Canada 

15. Emma Nicholls-Allison, University of Victoria, Canada 

16. Hisashi Miyamoto, Kyoto University, Japan 

17. Antonín Lyčka, University of Pardubice, Czech Republic 

18. Roman Jambor, University of Pardubice, Czech Republc 

19. Libor Dostál, University of Pardubice, Czech Republic 

20. Guoxiong Hua, University of St. Andrews, UK 

21. Masaichi Saito, Saitama University, Japan 

22. Louise Diamond, University of St. Andrews, UK 

23. Laura Forfar, University of Bristol, UK 

24. José Manuel Villalba Franco, Rheinische Friedrich-Wilhelms Universität Bonn, Germany 

25. Johanna Flock, Graz University of Technology, Austria 

26. Petra Wilfling, Graz University of Technology, Austria 

27. Eliza ter Jung, Philipps-University Marburg, Germany 

28. Bastian Weinert, Philipps-University Marburg, Germany 

29. Vojtech Jancik, Centro Conjunto de Investigación en Química Sustentable, Mexico 

30. Thomas Zöller, Technische Universität Dortmund, Germany 

31. Andreas Nordheider, University of St. Andrews, UK and University of Calgary, Canada 

32. Phillip Elder, University of Calgary, Canada 

33. Jonathan Dube, Western University, Canada 

34. Elizabeth MacDonald, Dalhousie University, Canada 

35. Jens Eußner, Philipps-Universität Marburg, Germany 

36. Alexandra Slawin, University of St. Andrews, UK 

37. Stewart Lucas, University of Victoria, Canada 

38. Yi-Chou Tsai, National Tsing-Hua University, Taiwan 

39. Takuya Kuwabara, Saitama University, Japan 

40. Derek Woollins, University of St. Andrews, UK 

41. Glen Briand, Mount Allison University, Canada 

42. Jamie Ritch, University of Winnipeg, Canada 

12 


Contributed Poster Presentations (continued) 

Poster Session B, Tuesday 31 July, 5:10 p.m. – 7:30 p.m. 

43. Peter Lee, University of Victoria, Canada 

44. Beatrix Barth, Philipps-University Marburg, Germany 

45. Christoph Bolli, Bergische Universität Wuppertal, Germany 

46. Mathias Keßler, Bergische Universität Wuppertal, Germany 

47. Thao Tran, University of Windsor, Canada 

48. Khatera Hazin, University of British Columbia, Canada 

49. Jan Turek, University of Pardubice, Czech Republic 

50. Teemu Takaluoma, University of Oulu, Finland 

51. Roman Olejnik, University of Pardubice, Czech Republic 

52. Aino Eironen, University of Oulu, Finland 

53. Kazuhiko Nagura, Nagoya University, Japan 

54. Minna Karjalainen, University of Oulu, Finland 

55. Timothy King, University of Cambridge, UK 

56. Tomokatsu Kushida, Nagoya University, Japan 

57. Paresh Kumar Majhi, Rheinische Friedrich-Wilhelms Universität Bonn, Germany 

58. Arturo Espinosa, Universidad de Murcia, Spain 

59. Josef Binder, Graz University of Technology, Germany 

60. Andrew Priegert, University of British Columbia, Canada 

61. Hugh Cowley, University of Windsor, Canada 

62. Justin Wrixon, University of Windsor, Canada 

63. Christopher Allan, University of Windsor, Canada 

64. Krzysztof Radacki, Universität Würzburg, Germany 

65. Tom Hsieh, University of British Columbia, Canada 

66. Zdenka Padelkova, University of Pardubice, Czech Republic 

67. Dominik Naglav, Universität Duisburg-Essen, Germany 

68. Christian Hering, Universität Rostock, Germany 

69. Thomas Wilson, University of Cambridge, UK 

70. Lucia Myongwon Lee, McMaster University, Canada 

71. Adrian Houghton, University of Calgary, Canada 

72. Melina Klein, Rheinische Friedrich-Wilhelms Universität Bonn, Germany 

73. Saurabh Chitnis, University of Victoria, Canada 



76. Benjamin Rawe, University of British Columbia, Canada 

77. Johann Pichler, Graz University of Technology 

78. Jonathan Dube, Western University, Canada 

79. Joseph West, University of North Dakota, USA 

80. Mónica Moya-Cabrera, Universidad Nacional Autónoma de México, Mexico 

81. Rene Boeré, University of Lethbridge, Canada 

82. Vojtech Jancik, Centro Conjunto de Investigación en Química Sustentable, Mexico 

83. Thomas Zöller, Technische Universität Dortmund, Germany 

84. Sarah Dane, University of Cambridge, UK 

85. Tomas Chlupaty, University of Pardubice, Czech Republic 

13 


Plenary 1 Monday 9:00 a.m. 

14 


Stable Carbenes for the Stabilization of Organoboron Lewis Bases, Phosphino 

Nitrenes, and for the Activation of P4 

Guy Bertrand 

(guy.bertrand@ucr.edu) 

UCR/CNRS Joint Research Chemistry Laboratory, University of California, Riverside, CA, 92521, USA 

Amines and boranes are the archetypical Lewis bases and acids, respectively. We will discuss the 

synthesis of neutral tricoordinate boron derivatives A, which act as Lewis bases giving B, and undergo 

one-electron oxidation into the corresponding radical cations C. Compounds A, B and C are borylenes 

(R-B:), borynium (R2B + ) and borinylium (R-B +. ), respectively, stabilized by two carbenes. [1] 

Transition metal nitrido (or metallo nitrene) complexes LnMN have attracted considerable attention due to 

their implications in biological nitrogen fixation by the nitrogenase enzymes, the industrial hydrogenation 

of N2 into NH3, exemplified by the Haber- Bosch process, and more generally for catalytic nitrogen-atom 

transfer reactions. We will discuss the synthesis and reactivity of the first stable non-metallic nitrene. [2] 

Lastly, recent results concerning the carbene activation of white phosphorus will be discussed. [3] 

[1] R. Kinjo, B. Donnadieu, M. Ali Celik, G. Frenking, G. Bertrand, Science 2011, 333, 610-613. 

[2] F. Dielmann, O. Back, M. Elinger, G. Frenking, G. Bertrand, 2012, unpublished results. 

[3] D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389-399 

[4] For the coordination and activation of σ-bonds at coinage metals, see: a) P. Gualco, S. Ladeira, K. 

Miqueu, A. Amgoune, D. Bourissou, J. Am. Chem. Soc. 2011, 133, 4257; b) P. Gualco, S. Ladeira, 

K. Miqueu, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed. 2011, 50, 8320.

Keynote 1 Monday 9:40 a.m. 

15 


Coordination of Lewis Acids and σ-Bonds by a Chelating Approach: 

Towards Original Metallacycles 

D. Bourissou 

(dbouriss@chimie.ups-tlse.fr) 

Université Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée 

118 route de Narbonne, 31062 Toulouse cedex, France 

Over the last few years, our group has been studying the coordination properties of ambiphilic ligands. [1] 

Our approach consists in using donor groups, typically phosphines, to support original metal / ligand 

interactions. This strategy was first used to investigate the coordination of Lewis acids as σ-acceptor 

ligands (metallacycles of type A). [2] We are now extrapolating this approach to the coordination and 

activation of inert σ-bonds (metallacycles of type B). [3] 

In this presentation, recent examples of both types will be discussed. Particular attention will be devoted 

to the structure of the isolated metallacycles that will be analyzed on the basis of spectroscopic, 

crystallographic and computational data. 

[1] For a review on the coordination of ambiphilic ligands, see: G. Bouhadir, A. Amgoune, D. Bourissou, 

Adv. Organomet. Chem. 2010, 58, 1. 

[2] For a review on σ-acceptor ligands, see: A. Amgoune, D. Bourissou, Chem. Commun. 2011, 47, 859.

16 


Cyclic Imido-Selenium and -Tellurium Compounds and their Transition 

Metal Complexes 

Risto S. Laitinen, a Aino Eironen, a Raija Oilunkaniemi a and Tristram Chivers b 

(risto.laitinen@oulu.fi) 

a Department of Chemistry, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland, b Department of 

Chemistry, University of Calgary, 2500 University Drive N.W., Calgary, Alberta, T2N 1N4 Canada 

Recent progress in the chemistry of imido derivatives of selenium and tellurium is discussed in order to 

provide understanding in the unusual features of their structures, bonding, and reactivities. Structural 

trends are considered by including also comparisons with related sulfur-nitrogen compounds, where 

appropriate (for a recent review, see ref. 1). Cyclic sulfur imides form a well-characterized class of 

compounds the most common examples being the eight-membered ring molecules S8-n(NH)n. While the 

corresponding selenium and tellurium imides are unknown, some organic derivatives have been prepared 

and structurally characterized. 

Se3(NAd)2 Se3(N t Bu)3 Se6(N t Bu)2 Se9(N t Bu)6 

Te3(N t Bu)3 

The coordination chemistry of selenium and tellurium imides is also described. Metal complexes of 

selenium(IV) and tellurium(IV) diimides are exclusively N,N’-coordinated, whereas cyclic selenium 

imides behave as chelating Se,Se’-donor ligands. 

[PdCl2{Se(N t Bu)2}] 

[PtCl2{Se(N t Bu)2}] 


[HgCl2{ t BuNTe(µ-N t Bu)2TeN t Bu}] 

[CoCl2{ t BuNTe(µ-N t Bu)2TeN t Bu}] 

[PdCl2{Se4(N t Bu)3}] 

[PdCl2{Se4(N t Bu)4}] 

[1] Laitinen, R.S., Oilunkaniemi, R., Chivers, T., in Woollins, J.D., Laitinen, R.S. (ed.), Selenium and 

Tellurium Chemistry: From Small Molecules to Biomolecules and Materials, Springer Verlag, Berlin 

2011, pp. 103-122.


17 


"Take 2": An Elegant Approach To Multinary Metallates and Intermetalloid 

Clusters 

Stefanie Dehnen 

(dehnen@chemie.uni-marburg.de) 

Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität 

Marburg, Hans-Meerwein-Straße, D-35032 Marburg, Germany 

Multinary, non-oxidic metallates are currently actively investigated by many research groups, leading 

from structural studies through functional analyses to the generation of innovative materials. [1] Binary 

main group element aggregates proved to be useful synthetic tools for a large variety of different 

structural and functional motifs. [2] 

Whereas chalcogenido-tetrelate/trielate ions [TxChy] q– (T = Ge, Sn, In; Ch = S, Se, Te) may be basically 

viewed as heavier homologues of silicates or borates, the inversely polarized pnictogene-tetrelide/trielide 

ions [TxPny] q– (Pn = Sb, Bi) have a distinct tendency to form intermetalloid clusters. [3] 

However, in both cases, the products of reactions with further metal M compounds differ significantly 

from any lighter homologues, as they represent unprecedented, ternary clusters or networks, according to 

the general type [MxTyChz] q– , [(RT)xMyEz] (R = functional/bridging organic ligand) or ternary Zintl 

anions [MxTyPnz] q– . The physical properties of the compounds, which may represent (photo-)semiconductors, 

ion conductors or bond-activating nano-capsules, are dependent on the nature of the involved 

elements and the observed structure type. [4–6] Ionothermal techniques were successfully applied recently 

for the synthesis of novel salts of such complex anions. [7] 

[1] P. Feng, X. Bu, N. Zheng, Acc. Chem. Res. 2005, 38, 293. [2] S. Dehnen, M. Melullis, Coord. Chem. 

Rev. 2007, 251, 1259. [3] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168. [4] S. 

Haddadpour, M. Melullis, H. Staesche, C.R. Mariappan, B. Roling, R. Clérac, S. Dehnen, Inorg. Chem. 

2009, 48, 1689. [5] Z. Hassanzadeh Fard, M. Reza Halvagar, S. Dehnen, J. Am. Chem. Soc. 2010, 32, 

2848. [6] F. Lips, M. Hołyńska, R. Clerac, U. Linne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, 

J. Am. Chem. Soc. 2012, 134, 1181. [7] Y. Lin, W. Massa, S. Dehnen, J. Am. Chem Soc. 2012, 134, 4497.

Novel Ring Systems from Disilynes 

18 


Akira Sekiguchi 

(sekiguch@chem.tsukuba.ac.jp) 

Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 

Tsukuba, Ibaraki 305-8571, Japan 

The stable disilyne with a silicon-silicon triple bond bearing two bulky substituents, Si i Pr[CH(SiMe3)2]2 

groups have been prepared in our group, [1] and we reported a full characterization of the first isolable 

crystalline disilyne 1, RSi≡SiR (R = Si i Pr[CH(SiMe3)2]2), showing that the silicon–silicon triple bond is 

not linear, but trans-bent, which results in two nondegenerate occupied π-MOs and two unoccupied 

antibonding π*-MOs. [2,3] To understand the nature of the π-bonding of the silicon–silicon triple bond, we 

have investigated the reactivity of the disilyne 1 toward a variety of reactants, such as alkenes, alkynes, 

RLi (R = Me, 

Plenary 2 Monday 11:30 a.m. 

t Bu), alkali metals, nitriles, silyl cyanides, amines, hydroboranes, 1,3,4,5- 

tetramethylimidazol-2-ylidene, and 4-dimethylaminopyridine, azobenzenes, carbonyl compounds, which 

has opened a new field of unsaturated heavier Group 14 element chemistry. The reactivity of 1 for the 

construction of the novel ring systems will be reported. [4] 

[1] Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Science, 2004, 305, 1755. 

[2] Kravchenko, V.; Kinjo, R.; Sekiguchi, A.; Ichinohe, M.; West, R.; Balazs, Y. S.; Schmidt, A.; Karni, 

M.; Apeloig, Y. J. Am. Chem. Soc. 2006, 128, 14472. 

[3] Murata, Y.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2010, 132, 16768. 

[4] For the reactivity of 1, see: (a) Kinjo, R.; Ichinohe, M.; Sekiguchi, A.; J. Am. Chem. Soc. 2007, 129, 

26. (b) Kinjo, R.; Ichinohe, M.; Sekiguchi, A.; Takagi, N.; Sumimoto, M.; Nagase, S. J. Am. Chem. 

Soc. 2007, 129, 7766. (c) Takeuchi, K.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2008, 130, 

16848. (d) Yamaguchi, T.; Sekiguchi, A.; Driess, M. J. Am. Chem. Soc. 2010, 132, 14061. (e) 

Yamaguchi, T.; Sekiguchi, A. J. Am. Chem. Soc. 2011, 133, 7352. (f) Takeuchi, K.; Ichinohe, M.; 

Sekiguchi, J. Am. Chem. Soc. 2011, 133, 12478. (g) Yamaguchi, T.; Asay, M.; Sekiguchi, A. J. Am. 

Chem. Soc. 2012, 134, 836.

Oral 1 Monday 1:40 p.m. 

Acids of the Heavier p-Block Elements and Related Metalloxanes 

Jens Beckmann 

(j.beckmann@uni-bremen.de) 

Institute of Inorganic and Physical Chemistry, Bremen University, Bremen, Germany 

19 


Exploratory chemistry is presented of the novel p-block element acids 1-5, [1-4] which can be regarded as 

heavier congeners of sulfinic acids, sulfonic acids, phosphonic acids, carboxylic acids and boronic acids, 

respectively. In 1-5, kinetic stabilization was achieved using a bulky m-terphenyl substituent that prevents 

extensive aggregation. Attempts at obtaining similar acids by the electronic stabilization using an 

intramolecularly coordinating peri-N donor substituent were less effective and provided (partially) 

condensed polynuclear products, as exemplified by 6 and 7. [5] Reactions of 1-7 and related compounds 

gave rise to new inorganic heterocycles, such as 8-10. [6-8] 

[1] J. Beckmann, P. Finke, M. Hesse, B. Wettig Angew. Chem. Int. Ed. 2008, 47, 9982. 

[2] J. Beckmann, J. Bolsinger, M. Hesse, P. Finke Angew. Chem. Int. Ed. 2010, 49, 8030. 

[3] S. U. Ahmad, J. Beckmann, A. Duthie Chem. Asian J. 2010, 5, 160. 

[4] S. U. Ahmad, J. Beckmann Organometallics 2009, 28, 6893. 

[5] J. Beckmann, J. Bolsinger, A. Duthie Chem. Eur. J. 2011, 17, 930. 

[6] S. U. Ahmad, J. Beckmann, A. Duthie Organometallics 2012, 31, 3802. 

[7] J. Beckmann, J. Bolsinger, M. Hesse Organometallics 2009, 28, 4225. 

[8] J. Beckmann, M. Hesse Organometallics 2009, 28, 2345.

20 


Cyclometalation and Organometallic Intramolecular-coordination Fivemembered 

Ring Compounds as Universal Reagents 

I. Omae 

(um5i-oome@asahi-net.or.jp) 

Omae Research Laboratories, 335-23, Mizuno, Sayama, Saitama, 350 -1317, Japan 

Cyclometalation is a type of reactions capable of synthesizing organometallic intramolecular-coordination 

compounds. By the reactions, five-membered ring compounds are mostly produced. These products are 

mainly prepared by utilizing transition metal compounds. The first article on the transition metal 

compounds was reported in 1963 in that π-N=N electrons in azobenzene are donated to a nickel atom to 

form an intramolecular bond with UV and NMR spectra data. However, in 1965, it was reported that the 

intramolecular bond was the result of donation of nitrogen lone pair electrons in the azobenzene to a 

palladium or platinum metal with the UV and NMR spectra data. As the verification of the intramolecular 

coordination bond to these two contradictive reports, in 1989, it was reported that the intramolecular 

coordination was shown as the result of coordination of the nitrogen lone pair electrons to the metal atom, 

which is verified by IR, NMR spectra and X-ray diffraction data on two azobenzene chelate complexes. 

However, in 1966, before this verification, we already reported the clean verification on the 

intramolecular bond in organotin compounds as main group metal compounds in Japanese article [1] as 

follows: 

O 

2 BrCHCOH 

CH2COH O 

β 

γ 

O 

cat. 

β 

+ Sn Br2Sn CHCOH 

ν βC=O : 1740 cm -1 

ν γC=O : 1740 cm -1 


γ 

O 

C 

OH 

CH 2 

2 

ν βC=O : 1710 cm -1 

(shift = 30 cm -1 ) 

ν γC=O : 1660 cm -1 

(shift = 80 cm -1 ) 

Massive organometallic intramolecular-coordination five-membered ring compounds have been 

synthesized with not only N and O atoms but also P, As and S atoms as the coordinating atom, and 

furthermore with coordinating groups such as C=C, C=C-C, Cp, diolefins, etc. The reports on the 

organometallic intramolecular-coordination compounds having these ligand atoms and ligand groups 

have been published as many reviews [2,3] since 1971, and a monograph for them was published from 

Elsevier company in 1986 [4] . Especially, the organometallic intramolecular-coordination five-membered 

ring compounds are surprisingly easily and regioselectively synthesized by using many kinds of metal 

compounds and with many kinds of substrates. Hence, these reactions are applied as the synthesis of the 

final products and the intermediates, the products are used as catalysts for chiral reactions, metathesis 

reactions, cross-coupling reactions, etc., for the production of pharmaceuticals, fine chemicals, etc. [5] 

Hence, the number of the published research articles is more than 7 times than each of those related to the 

recent Nobel Prize in synthetic chemistry such as chiral catalysts (2001), metathesis (2005) and crosscoupling 

reactions (2010) from the Chemical Abstract Database SciFinder Scholar 2012, 1, 26 data. 

[1] S. Matsuda, S. Kikkawa, I. Omae, Kogyo Kagaku Kyokaishi, 1966, 69, 646. 

[2] I. Omae, Rev. Silicon, Germanium, Tin and Lead Compounds, 1971, 1, 59. 

[3] I. Omae, Chem. Rev. , 1979, 79, 287. 

[4] I. Omae, Organometallic Intramoledular-coordination Compounds, Elsevier, Amsterdam, 1986. 

[5] I. Omae, Coord. Chem. Rev. 2004, 248, 995; J. Organomet. Chem. 2007, 692, 2608.


21 


Activation and Transformation of Phosphorus-Rich Rings and Cages 

M. Scheer, F. Dielmann, S. Welsch, C. Heindl, S. Heinl, C. Schwarzmaier 

(manfred.scheer@chemie.uni-regensburg.de) 

Institute of Inorganic Chemistry, University of Regensburg, Germany 

Polyphosphorus species and moieties play an important role in contemporary main group and transition 

metal chemistry. The talk will focus on two related areas of research: (i) the development of novel starting 

materials for E4 transfer reactions (E = P, As) and to acquire novel synthetic concepts of activation of 

white P4 and yellow As4. (ii) the use of substituent-free polyphosphorus ligand complexes in an 

alternative supramolecular approach. 

The first topic deals with the synthesis of novel Ag and Zr complexes containing activated Pn and Asn 

units (n ≤ 4). These compounds can be used as unique reagents to transfer En moieties to transition metals 

under very mild conditions. Moreover, a novel concept for the aggregation of tetrahedral E4 by transition 

metal compounds is presented resulting in neutral En-rich complexes. [1] 

In the second part the chemistry of the cyclo-P5 containing complex [Cp*Fe(η 5 -P5)] is discussed. On one 

hand it can be transferred by redox-reactions into ionic P-rich complexes. On the other hand it shows 

unique supramolecular properties since under special conditions it forms together with Cu(I) halides 

soluble spherical aggregates and supramolecules. [2] By using carboranes or fivefold-symmetric 

organometallics as a third component soluble giant spheres revealing fullerene-like topology are formed 

as a consequence of template controlled reactions. [3] The approach to an organometallic nano-sized 

capsule consisting of cyclo-P5 units and Cu(I) ions is further presented. [4] 

[1] F. Dielmann, M. Sierka, A. V. Virovets, M. Scheer, Angew. Chem. 2010, 122, 7012–7016; Angew. 

Chem. Int. Ed. 2010, 49, 6860–6864. 

[2] M. Scheer, Dalton Trans. 2008, 4372–4386. 

[3] A. Schindler, C. Heindl, G. Balázs, C. Gröger, A. V. Virovets, E. V. Peresypkina, M. Scheer, Chem. 

Eur. J. 2012, 18, 829–835. 

[4] S. Welsch, C. Gröger, M. Sierka, M. Scheer, Angew. Chem. 2011, 123, 1471–1474; Angew. Chem. 

Int. Ed. 2011, 50, 1435–1438.


22 


Synthesis and Characterization of Heterocyclic Silicon Based Push-Pull 

Systems 

Uwe Walter Gross and Harald Stueger 

(uwe.gross@tugraz.at) 

Institute of Inorganic Chemistry, Graz University of Technology, Austria 

Donor-acceptor (D-A) interactions within various types of D-spacer-A compounds are currently studied 

extensively in order to address key issues like electron transfer processes, artificial photosynthesis or 

molecular devices. [1] In this context silicon based oligo- and polysilanes display attractive electronic 

properties which result from delocalized σ-electrons along the silicon backbone (σ-delocalization). [2] σdelocalization 

is particularly pronounced in cyclic Si-Si- bonded systems. Cyclopolysilane rings and 

cages, therefore, are likely to serve as effective σ-conjugated bridges in bichromophoric covalently linked 

donor-bridge-acceptor compounds. In this work we present synthetic routes to novel cyclohexasilanes, 

which contain endocyclic donor atoms and acceptor substituents in para positions. 

Figure 1: Synthetic pathway leading to functionalized heterocyclopolysilanes 

Photophysical and electrochemical properties of the heterocyclic compounds 5 will be investigated in 

detail in order to shed light on the extent of intramolecular donor/acceptor interactions via the Si-Si 

skeleton. 

[1] Y. Shirota, H. Kageyama, Chem. Rev. 2007, 107, 953-1010. 

[2] R. West, Pure Appl. Chem. 1982, 54, 1041-1050.


23 


Reactions of Cyclodimethylsiloxanes (Me2SiO)n with Silver Salts and 

Rationalization for Weaker Lewis Basicity of Siloxanes Compared to Ethers 

T. Stanley Cameron, a Andreas Decken, b Ingo Krossing, c Jack Passmore, b J. Mikko Rautiainen, d Xinping 

Wang, e Xiaoqing Zeng f 

(juha.rautiainen@oulu.fi) 

a Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3, Canada 

b Department of Chemistry, University of New Brunswick, Fredericton, NB E3B 5A3, Canada 

c Institute for Inorganic and Analytical Chemistry, Albert–Ludwigs–Universität Freiburg, Albertstr. 21, 

79104 Freiburg, Germany 

d Department of Chemistry, P. O. Box 3000, 90014 University of Oulu, Finland 

e State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P.R.China 

f Division C – Inorganic Chemistry, University of Wuppertal, Gaußstr. 20, 42119 Wuppertal, Germany 

Reactions of cyclodimethylsiloxanes (Me2SiO)m (m = 3-6) with Ag[SbF6] in SO2(l) have been shown to 

give equilibrium mixtures of mainly AgDn[SbF6] (n = 6-8) complexes and afford the isolation of 

[AgD7][SbF6] salt. [1] In contrast reactions of D6 with Ag[Al(ORF)4] and Ag[AlF(ORF)3] in SO2(l) give the 

corresponding AgD6 + complex salts. This suggests alternative routes to metal cyclodimethylsiloxane 

complex salts either via ring transformation reactions or directly from components. The energetics of 

metal cyclodimethylsiloxane complex formation and 

relative stabilities of different complexes will be 

discussed in the presentation. 

The differences of bonding between siloxanes and 

ethers and reasons for the lower basicity of siloxanes 

will be elucidated on the basis of the observed 

structures and theoretical calculations. Our results 

show that the inherently weaker binding of siloxanes 

towards metal cations compared to analogous ethers is 

mainly due to the high polarity of the silicon oxygen 

bond that causes high positive atomic charges on 

silicon atoms and repulsion between silicon atoms and 

metal ions. This repulsion outweighs the stronger 

binding between metal ions and the more negatively 

charged oxygen atoms in siloxanes. 

Figure 2 [AgD6] + 

[1] Decken, A., LeBlanc, F. A., Passmore, J., Wang, X., Eur. J. Inorg. Chem. 2006, 4033.

24 


Novel Four- and Five-membered Binary Pnictogen-Nitrogen-Rings: 

From Neutral Biradicals to cyclo-Dipnicta-Diazenium Ions 

Axel Schulz a,b 

(axel.schulz@uni-rostock.de) 

a Institut für Chemie, University of Rostock, b Leibniz-Institut für Katalyse e.V., A.-Einstein-Str. 3A 18059 

Rostock, Germany 

Four-membered rings of the type [XE(µ-NR)]2 (Scheme 1, species B), containing alternating 

pnictogen(III) and nitrogen centers, are called cyclo-1,3-dipnicta(III)-2,4-diazanes (X = halogen, R = 

bulky substituent). [1,2] This talk deals with the syntheses and full characterization of the whole series of 

salts bearing the cyclo-dipnicta-diazenium ions (Scheme 1, species C for E = P, As, Sb, and Bi). [3] A new 

facile synthetic approach is presented for the preparation of the Bi- and Sb-species B by transmetallation 

reaction starting from [Sn(�-NTer)]2. [4] Access to the hitherto unknown biradicaloid species D (E = P, [5] 

and As [3c] ) is easily obtained by reduction with Cp2Ti(btmsa) (btmsa = bistrimethylsilylacetylene). 

Finally, besides tetrazaphosphols and -arsols, the tetraazastibol (species F) is presented, which could be 

isolated in an unusual isomerization process starting from cyclo-1,3-distiba(III)-2,4-diazane B and a 

strong Lewis acid such as B(C6F5)3. [6] Moreover, for the As analogue it was possible to isolate und fully 

characterize the R–N≡As + species E bearing a triple bond, and to react E with Me3SiN3 to tetrazaarsole 

F. [3c,7] 

R 

N E 

1/2 

E N 

D R 

+2e - 

-2X - 

R X 

N E 

1/2 

E N 

X B R 

+LA 

R 

N E 

1/2 LA-X 

E N 

X C R 


R 

N E 

A 

X 

LA 

N E 

E 

+Me3SiN3 -Me3SiX E 

R LA 

N N 

N N 

F 

[1] M. S. Balakrishna, D. J. Eisler, T. Chivers, Chem. Soc. Rev. 2007, 36, 650. 

[2] L. Stahl, Coord. Chem. Rev. 2000, 210, 203. 

a) D. Michalik, A. Schulz, A. Villinger, N. Weding, Angew. Chem., Int. Ed. 2008, 47, 6465; b) 

A. Schulz, A. Villinger, Inorg. Chem. 2009, 48, 7359; c) submitted 2012. 

[3] W. A. Merrill, R. J. Wright, C. S. Stanciu, M. M. Olmstead, J. C. Fettinger, P. P. Power, Inorg. 

Chem. 2010, 49, 7097. 

[4] T. Beweries, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2011, 50, 

8974. 

[5] M. Lehmann, A. Schulz, A. Villinger, Angew. Chem., Int. Ed. 2011, 50, 5221. 

[6] A. Schulz, A. Villinger, Angew. Chem., Int. Ed. 2008, 47, 603. 

R 

LA-X 

+Me 3SiN 3 

+LA 

-Me 3SiX 

LA = Lewis acid 

X = halogen 

R = bulky substituent


Thiazyl and Selenazyl Heterocycles as Paramagnetic Ligands 

Kathryn E. Preuss 

(kpreuss@uoguelph.ca) 

Department of Chemistry, University of Guelph, Guelph, ON N1G 2W1, Canada 

25 


Our aim is to exploit the properties of well-known thiazyl and selenazyl radicals for use in the design of 

paramagnetic ligands. By arranging these main-group structures into familiar ligand architectures, we 

endeavor to contribute a variety of novel, paramagnetic ligands and coordination complexes with unusual 

and potentially useful properties. [1] Specifically, we will present ligands that incorporate 1,2,3,5dithiadiazolyl 

(DTDA) and 1,2,5-dithiazolyl (DTA) heterocycles, and their selenazyl analogs. 

Coordination complexes of these with 3d transition metal dications (M 2+ ) and lanthanide metal trications 

(Ln 3+ ) will be discussed. Examples that will be highlighted include a DTDA complex of Mn 2+ that forms 

high spin pairs in the solid state, [2] dimers of DTDA Dy 3+ complexes that act as single-molecule magnets 

(SMM)s, and Gd 3+ polymers of a DTA ligand. 

[1] Wu, J.; MacDonald, D. J.; Clérac, R.; Jeon, I.-R.; Jennings, M.; Lough, A. J.; Britten, J.; Robertson, 

C.; Dube, P. A.; Preuss, K. E.* Inorg. Chem. 2012, 51, 3827-3839. 

[2] Fatila, E. M.; Goodreid, J.; Clérac, R.; Jennings, M.; Assoud, J.; Preuss, K. E.* Chem. Commun. 2010, 

46, 6569.

26 


Recent Advances in the Chemistry of N-Heterocyclic Diphosphines 

Dietrich Gudat, Daniela Förster, Oliver Puntigam, Jan Nickolaus and Martin Nieger 

(gudat@iac.uni-stuttgart.de) 

Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart, Germany 

Tetraamino-substituted diphosphines featuring both acyclic (I) and cyclic (II) diphosphanyl units are well 

known to undergo homolytic P–P-bond cleavage to give long-lived phosphanyl radicals: [1,2] 

(R'RN) 2P P(NRR') 2 2 (RR'N) 2P 

I 

R 

N 

R 

N 

P P 

N 

R 

II 

N 

R 


2 

Starting from an improved synthesis which gives access to both bis-diazaphospholenyls II and the appropriate 

CC-saturated bis-diazaphospholidines III we present recent results on the structural and spectroscopic 

characterization of these species, including the determination of 1 JP,P coupling constants in 

symmetrical derivatives II, III where the two phosphorus atoms exhibit apparently total magnetic 

equivalence. Monitoring the equilibrium between bis-diazaphospholenyl IIc (R = 2,6-iPr2C6H3) and the 

corresponding radical by NMR and EPR spectroscopy allowed further to gather mechanistic information 

on the diphosphine dissociation, and to obtain experimental data which allow to assess the energetics of 

the homolytic P–P bond cleavage process. Comparison of the experimental data with the results of 

thermochemical calculations suggests the importance of including correlation and dispersion effects in the 

computational model. 

The ability to access N-heterocyclic diphosphines II, III on a preparative scale stimulated further studies 

of their chemical properties. As the first results of these investigations, we will report on the addition of 

II, III to multiple bonds, and the characterization of pseudo-homoleptic phosphenium-metal(0)halides 

[(NHP)2MCl]2 (NHP = N-heterocyclic phosphenium; M = Pd, Pt). The metal atoms in these specimen are 

not supported by additional donor ligands but feature according to computational studies direct bonding 

interaction between centers with a formal d 10 electron count. 

[1] Gynane, M. J. S.; Hudson, A.; Lappert, M. F.; Power, P. P.; Goldwhite, H. Chem. Commun. 1976, 

623; Gynane, M. J. S.; Hudson, A.; Lappert, M. F.; Power, P. P.;Goldwhite, H. Dalton Trans. 1980, 

2428; Bezombes, J.-P.; Hitchcock, P. B.; Lappert, M. F.; Nycz, J. E., Dalton Trans. 2004, 499; 

Bezombes, J.-P.; Borisenko, K. B.; Hitchcock, P. B.; Lappert, M. F.; Nycz, J. E.; Rankin, D. W. H.; 

Robertson, H. E., Dalton Trans. 2004, 1980. 

[2] Edge, R.; Less, R. J.; McInnes, E. J. L.; Müther, K.; Naseri, V.; Rawson, J. R.; Wright, D. S., Chem. 

Commun. 2009, 1691. 

R 

N 

P 

N 

R 

R 

N 

P 

N 

R 

III 

R 

N 

P 

N 

R


Boroles going Radical: An Isolable Radical Anion 

27 


Johannes Wahler and Holger Braunschweig 

(johannes.wahler@uni-wuerzburg.de) 

Institute of Inorganic Chemistry, Julius-Maximilians-University Würzburg, Am Hubland, 97074 

Würzburg, Germany 

The concepts of aromaticity and antiaromaticity have evolved into some of the fundamental principles of 

chemistry. Today, numerous experimental and theoretical techniques are available to substantiate the 

effect of aromatic stabilization and antiaromatic destabilization. Isolation of antiaromatic compounds, 

however, still remains challenging as a consequence of their highly reactive nature. The synthesis of free, 

non-annulated boroles, first reported by J. J. Eisch in 1969, showed that inclusion of a sp 2 hybridized 

B−R fragment into a planar conjugated carbacyle is a suitable strategy to approach this purpose. [1] 

Subsequent experiments and computational results verified not only the antiaromatic character of boroles 

(four π-electrons) but also the aromatic character of borole dianions (six �-electrons) generated by 

chemical reduction of the system. [2,3] 

In recent studies we showed that reduction of boroles proceeds stepwise involving an intermediate borole 

radical anion (five π-electrons) which could so far only be characterized by spectroscopic methods from 

in situ generated substance. [4] Synthesis of 1-mesityl-2,3,4,5-tetraphenylborole (1) allowed us to prepare a 

stable borole radical anion (2), which we have characterized by means of computational methods, EPR 

spectroscopy, X-ray crystallography, UV-Vis spectroscopy and a first reactivity assay. Our results 

indicate the presence of a boron-centered radical with pronounced spin delocalization within the borole 

annulus rather than to the exo-cyclic aryl groups. [5] 

[1] J. J. Eisch, N. K. Hota, S. Kozima, J. Am. Chem. Soc. 1969, 91, 4575−4577. 

[2] H. Braunschweig, I. Fernández, G. Frenking, T. Kupfer, Angew. Chem. Int. Ed. 2008, 47, 1951−1954. 

[3] J. J. Eisch, J. E. Galle, S. Kozima, J. Am. Chem. Soc. 1986, 108, 379−385. 

[4] H. Braunschweig, F. Breher, C.-W. Chiu, D. Gamon, D. Nied, K. Radacki, Angew. Chem. Int Ed. 

2010, 49, 8975−8978. 

[5] H. Braunschweig, V. Dyakonov, J. O. C. Jimenez-Halla, K. Kraft, I. Krummenacher, K. Radacki, A. 

Sperlich, J. Wahler, Angew. Chem. Int. Ed. 2012, 51, 2977−2980.


Polychalcogen Macrocycles Supported by P2N2 Rings 

28 


Andreas Nordheider, a,c Tristram Chivers, a Ramalingam Thirumoorthi, a Ignacio Vargas-Baca b and J. Derek 

Woollins c 

(chivers@ucalgary.ca) 

a Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada 

b Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St. W., Hamilton, 

ON, Canada, L8S 4M1 

c Department of Chemistry, University of St Andrews, St Andrews UK, KY16 9ST 

An oxidative strategy has been successful for the generation of a variety of dichalcogenides with acyclic 

or spirocyclic structures from the corresponding dichalcogenido PNP-bridged monoanions. [1] Application 

of this methodology to the known P2N2-bridged dianions [EP2N2E] 2- [E = S, Se, Te: P2N2 = ( t BuN)P(μ- 

N t Bu)2P(N t Bu)] [2,3] produces novel polychalcogen macrocycles, e.g. the trimers [-P2N2-(μ-E-E-)]3 (E = S, 

Se) in which a planar P6E6 motif incorporating dichalcogenido groups is stabilized by P2N2 scaffolds. [4] 

The NMR spectra (solution and solid state) and X-ray structures of these novel polychalcogen 

macrocycles will be discussed in the context of DFT calculations. The extension of this chemistry to the 

formation of phosphorus-tellurium rings will also be 

described. 

[1] For a review, see T.Chivers, J. S. Ritch, S. E. Robertson, J. Konu and H. M. Tuononen, Acc. Chem. 

Res. 2010, 43, 1053. 

[2] T. Chivers, M. Krahn, M. Parvez and G. Schatte, Inorg. Chem., 2001, 40, 1493. 

[3] G. Briand, T. Chivers and M. Parvez, Angew. Chem. Int. Ed., 2002, 41, 3468. 

[4] A. Nordheider, T. Chivers, R. Thirumoorthi, I. Vargas-Baca and J. D. Woollins, Chem. Commun., 

2012, 48, 6346.


29 


Molecular Compounds with Bonds Between Heavier Group 15 Elements, 

Synthesis, Structures and Properties 

C. von Hänisch and S. Traut 

(haenisch@chemie.uni-marburg.de) 

Philipps-Universität-Marburg, Germany 

Homoatomic ring and cage compounds of the group 15 elements are well known for several years, [1] 

whereas heteroatomic rings and cages of these elements are rarely described in literature. Recently, 

Burford and co-workers reported some cationic compounds with bonds between different group 15 

elements. [2] In this talk, our results on the synthesis of neutral molecular compounds with bonds between 

heavier group 15 elements will be presented. Such species were obtained from the reaction of silyl or 

lithium functionalised phosphines or arsines with metal chlorides such as ECl3 or RECl2 (E = As, Sb, Bi; 

R = (Me3Si)2CH, (Me3Si)3C). [3] 

Figure 1 Molecular structures of the compounds [tBu2PhSiAs{BiClCH(SiMe3)2}2] (left) and 

[As2{BiClCH(SiMe3)2}4] (right) obtained from the reaction of (Me3Si)2CHBiCl2 with 

tBu2PhSiAs(SiMe3)2 and As(SiMe3)3, respectively. 

[1] a) M. Baudler, Angew. Chem. 1987, 99, 429-451; b) L.Balázs, H. J. Breunig, Coord. Chem. Rev. 

2004, 248, 603-621; c) M. Westerhausen, S. Weinrich, P. Mayer, Z. Anorg. Allg. Chem. 2003, 629, 

1153-1156; d) G. Linti, W. Köstler, Z. Anorg. Allg. Chem. 2002, 628, 63-66. 

[2] a) E. Conrad, N. Burford, R. McDonald, M. J. Ferguson, Inorg. Chem. 2008, 47, 2952-2954; b) E. 

Conrad, N. Burford, R. McDonald, M. J. Ferguson, J. Am. Chem. Soc. 2009, 131, 5066-5067; c) E. 

Conrad, N. Burford, R. McDonald, M. J. Ferguson, Chem. Commun. 2010, 46, 4598-4560. 

[3] a) D. Nikolova, C. von Hänisch, Eur. J. Inorg. Chem. 2005, 378-382; b) C. von Hänisch, D. 

Nikolova, Eur. J. Inorg. Chem. 2006, 4770-4773; c) C. von Hänisch, S. Stahl, Z. Anorg. Allg. 

Chem. 2009, 635, 2230-2235; d) S. Traut, A. P. Hähnel, C. von Hänisch, Dalton Trans. 2011, 40, 

1365-1371.


Manipulation of Low Coordinate Phosphorus Environments 

N. S. Townsend and C. A. Russell 

(nell.townsend@bristol.ac.uk) 

School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK 

30 


Main group chemistry which mimics that of carbon is key to expanding the boundaries of both inorganic 

and organic chemistry. The isolobal relationship between a CH moiety and a P atom has been used in 

predicting and rationalizing many novel compounds. Tert-butylphosphaalkyne, P≡C t Bu, is commonly 

worked with due to its relative ease of synthesis on a large scale and its isolobal relationship to an alkyne, 

which of course are abundant, versatile substrates in organic synthesis. [1] As with alkynes, oligomerisation 

can occur and one particular oligomer of interest is 2,4,6-tri-tertbutyl-1,3,5-triphosphabenzene. These sixmembered 

rings with aromatic character are isolobal to benzene and thus would be expected to mimic the 

diverse chemistry of the prototypical aromatic compound. However, the presence of phosphorus in the 

aromatic ring leads to additional reaction possibilities such as coordination through the phosphorus lone 

pair. 

Figure 3 Novel species derived from 2,4,6-tri-tertbutyl- 1,3,5-triphosphabenzene. 

The work presented expands upon the coordination of this interesting ligand, demonstrating the unusual 

ŋ 1 coordination mode. [2,3] Furthermore, the addition of reactive main group moieties based on pnictenium 

ions, which are isolable to carbenes, is investigated leading to rare examples of cationic P/C cages. Novel 

P/C cages are also accessible via the reaction of P≡C t Bu with these reactive pnictenium species. 

[1] Becker, G.; Schmidt, H.; Uhl, G.; Uhl, W., Inorg. Synth. 1990, 27, 243. 

[2] Clenndenning, S. B.; Hitchcock, P. B.; Nixon, J. F., Chem. Commun. 1999, 1377. 

[3] Townsend, N. S.; Green, M.; Russell, C. A., Organometallics, 2012, 31, 2543.


Bond-Selective Cleavage in Oxaphosphirane Complexes 

Rainer Streubel 

(r.streubel@uni-bonn.de) 

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn 

Gerhard-Domagk Str. 1, 53121 Bonn, Germany 

31 


Whereas unligated oxaphosphiranes possessing a σ 3 λ 3 -phosphorus (I) are still unknown, their com-plexes 

II have been reported in the early nineties. [1,2] The development of a new and facile protocol for the 

synthesis of oxaphosphirane complexes using Li/Cl phosphinidenoid complexes [3] paved the way to a 

broad systematic study and, hence, a wealth of new structures became available. 

This report will present the scope of this methodology [4] including investigations of reaction courses that 

lead to oxaphosphirane complexes. Furthermore, we will address the problem of bond-selective reactions 

of complexes II using various substrates [5] while focussing on endocyclic bonds (i-iii). In the last part, we 

will present first investigations on exocyclic bond cleavages (iv-v) in II, [6] thus entering the new areas of 

P-functional complexes (via iv) and free oxaphosphiranes (via v). Further-more, we will provide first 

examples of deoxygenation processes of complexes II which formally represent a combination of i) and 

ii). [7] 

Scheme: Oxaphosphiranes I and complexes II (M = Cr-W; R 1 = alkyl; R 2 , R 3 = alkyl, aryl) 

[1] Bauer, S.; Marinetti, A.; Ricard, L.; Mathey, F.; Angew. Chem. 1990, 102, 10, 1188. 

[2] Streubel, R.; Kusenberg, A.; Jeske, J.; Jones, P. G.; Angew. Chem. 1994, 106, 2564. 

[3] a) Özbolat-Schön, A.; von Frantzius, G.; Marinas Pérez, J.; Nieger, M.; Streubel, R.; Angew. Chem. 

Int. Ed. 2007, 46, 9327; b) Bode, M.; Daniels, J.; Streubel, R.; Organometallics 2009, 28, 4636. 

[4] a) Streubel, R.; Bode, M.; Marinas Pérez, J.; Schnakenburg, G.; Daniels, J.; Jones, P. G.; Z. Anorg. 

Allg. Chem. 2009, 635, 1163; b) Albrecht, C.; Bode, M.; Marinas Pérez, J.; Schnakenburg, G.; 

Streubel, R.; Dalton Trans. 2011, 40, 2654; c) Marinas Pérez, J.; Klein, M.; Kyri, A.; Schnakenburg, 

G.; Streubel, R.; Organometallics 2011, 30, 5636; d) Streubel, R.; Schneider, E.; Schnakenburg, G.; 

submitted. 

[5] a) Helten, H.; Marinas Pérez, J.; Schnakenburg, G.; Streubel, R.; Organometallics, 2009, 28, 1221; 

b) Marinas Pérez, J.; Helten, H.; Donnadieu, B.; Reed, C. A.; Streubel, R.; Angew. Chem. Int. Ed. 

2010, 49, 2615; c) Marinas Pérez, J.; Albrecht, C.; Helten, H.; Schnakenburg, G.; Streubel, R.; 

Chem. Commun. 2010, 46, 7244; d) Marinas Pérez, J.; Helten, H.; Schnakenburg, G.; Streubel, R.; 

Chem. Asian J. 2011, 6, 1539. 

[6] Espinosa, A.; Streubel, R.; submitted. 

[7] Albrecht, C.; Shi, L.; Marinas Pérez, J.; van Gastel, M.; Schwieger, S.; Neese, F.; Streubel, R.; 

submitted.


32 


Insights into the Mechanisms of Metal-Free Hydrogen Transfer between 

Amine-Boranes and Aminoboranes and Diborazane Redistribution: 

Implications for Polyaminoborane Synthesis 

Erin M. Leitao, Alasdair P. M. Robertson, Naomi E. Stubbs, Guy C. Lloyd-Jones, and Ian Manners 

(chzeml@bristol.ac.uk, ian.manners@bristol.ac.uk) 

School of Chemistry, University of Bristol, Cantock’s Close, BS8 1TS, UK 

Over the past decade, the development of amine-borane (RR’NH·BH 3, R = R’ = H or alkyl) 

dehydrogenation chemistry has accelerated due to the use of these adducts as precursors to boron-nitrogen 

containing polymers, in addition to their potential as hydrogen storage and transfer materials. [1] 

Polyaminoboranes, [RHN-BH2]n (R = alkyl), isoelectronic analogues of linear polyolefins [RHC-CH2]n, 

one of the most important synthetic polymers today, are an exciting class of main-group polymers with 

potentially interesting properties. These polymers have recently become accessible from a limited range 

of amine-borane adducts, facilitated by an iridium catalyst under mild conditions. [2] However, in order to 

increase the scope through polymerization of a wider variety of monomers, the mechanism of catalysis 

must be fully probed and understood. This is explored by studying simpler systems, such as the 

remarkable metal-free hydrogen transfer between aminoboranes (RR’N=BH2, R = R’ = alkyl) and amineboranes 

as well as model linear diborazanes (RR’NH-BH2-NRR’-BH3, R = R’ = H or alkyl), at room 

temperature, thermolytically, and catalytically. [3] This presentation will communicate pertinent 

mechanistic details of the hydrogen transfer and redistribution processes, relevant to the formation of 

polyaminoboranes. 

iPr 2N=BH 2 

+ 

Me 2NHįBH 3 

iPr2NHįBH3 + 

Me2N-BH2 iPr2NHįBH2 + 

1 /2[Me2N-BH2] 2 

MeNH 2-BH 2-NHMe-BH 3 MeNH 2įBH 3 + MeNH=BH2 

[1] Staubitz, A. et al. Chem. Rev. 2010, 110, 4023. Whittell, G.; Manners, I. Angew. Chem. Int. Ed. 2011, 

50, 10288. Staubitz, A. et al. Chem. Rev. 2010, 110, 4079. 

[2] Staubitz, A. et al. Angew. Chem. Int. Ed. 2008, 47, 6212. Staubitz, A. et al. J. Am. Chem. Soc. 2010, 

132, 13332. 

[3] Robertson, A. P. M. et al. J. Am. Chem. Soc. 2011, 133, 19322.


33 


Chemistry of Dimolybdaheteroboranes Containing group 16 Elements 

Kiran Kumar Varma Chakrahari and Sundargopal Ghosh 

(sghosh@iitm.ac.in) 

Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India 

Pyrolysis of [(Cp * Mo)2B4H8], (Cp * = η 5 -C5Me5), a possible intermediate generated by the reaction of 

[Cp * MoCl4] and [LiBH4.thf] at -40 ºC, with chalcogen sources yielded [(Cp * Mo)2B4H6E], (where E = S, 

Se and Te). Cluster [(Cp * Mo)2B4H6E] on reaction with [Fe2(CO)9] led to the formation of 

[(Cp * Mo)2B4H6EFe(CO)3]. Further, a new class of metallaheteroborane clusters, oblatocloso- 

[(Cp * Mo)2B3H3S(µ-CO)3Co2(CO)3] and hypoelectronic [(Cp * Mo)2B4H4S(µ3-CO)Co2(CO)4] have been 

isolated from the reaction of [(Cp * Mo)2B4H6E] with [Co2(CO)8]. The geometry of cluster 

[(Cp * Mo)2B3H3S(µ-CO)3Co2(CO)3] is unique, which can be generated from a 8 vertex closododecahedron 

by performing two diamond-square-diamond (dsd) rearrangements. The key results of this 

work will be discussed. 

[1] Aldridge, S.; Shang, M.; Fehlner, T. P. J. Am. Chem. Soc. 1998, 120, 2586. 

[2] Dhayal, R. S.; Chakrahari, K. K. V.; Varghese, B.; Mobin, S. M.; Ghosh, S. Inorg. Chem. 2010, 49, 

7741. 

[3] Chakrahari, K. K. V.; Ghosh, S. J. Chem. Sci. 2011, 123, 847.


34 


Transition Metal Anion Reagents for the Preparation of Inorganic and 

(Phospha)organometallic Ring Systems 

Robert Wolf, a,b Eva-Maria Schnöckelborg, b Jennifer Malberg a and Katharina Weber b 

(robert.wolf@ur.de) 

a University of Regensburg, Institute of Inorganic Chemistry, Universitätsstr. 31, 93053 Regensburg, 

Germany 

b University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 30, 48149 

Münster, Germany 

Our research group investigates anionic polyarene transition metal complexes that may be used as 

synthetic equivalents of transition metal anions. Only few representatives of this promising class of 

compounds have previously been reported. [1] In this contribution, we describe the synthesis and 

characterisation of the new iron complex [K(18-Krone-6){Cp*Fe(η 4 -C10H8)}] (1, Cp* = C5Me5). [2] 

Selected synthetic applications of this complex and related metalates are discussed. The synthetic 

potential of such reagents is demonstrated by the reaction of „Cp*Fe − equivalent” 1 with white 

phosphorus, which gave unusual anionic polyphosphido iron complexes 2 and 3 under mild conditions. [3] 

[1] a) Review: J. E. Ellis, Inorg. Chem. 2006, 45, 3167-3186; b) recent examples: R. E. Jilek, M. Jang, E. 

D. Smolensky, J. D. Britton, J. E. Ellis, Angew. Chem. Int. Ed. 2008, 47, 8692-8695, and refs. 

therein. 

[2] R. Wolf, E.-M. Schnöckelborg, Chem. Commun. 2010, 46, 2832-2834. 

[3] E.-M. Schnöckelborg, J. J. Weigand, R. Wolf, Angew. Chem. Int. Ed. 2011, 50, 6657-6660.


35 


Synthesis and Characterization of Ligand-Modified Aluminium Alkoxide 

Hameed Ullah Wazir †‡ and Michael Veith † 

(hameedwazir@yahoo.co.uk) 

† Institute of Inorganic and General Chemistry, University of Saarland, 66125 Saarbruecken Germany 

‡ Department of Chemistry Hazara University Mansehra 21300, KPK, Pakistan 

Development of designed molecular compounds of metals is of significant interest as single source 

precursors (SSPs) in material synthesis, specifically in synthesis of functional metal oxides. However, 

certain variable parameters hinder the development of the designed compounds. These variables include 

reaction temperature and time, nature of central metal atoms, solvents and ligands etc. Therefore, it is 

reasonable to say that a good control over these parameters assures the materialization of the designed 

SSPs. We have tested this hypothesis by synthesizing liagand-modified aluminum alkoxides of the 

general formula, [XxAl(OR)y-x]n, where X = H ˉ (1, 2) and Cl ˉ( 3), R=cyclohexyl (1, 2) and 1methylcyclohexyl 

(3), x varies from 1-2 and n=2 (3), 5 (1) and n (2) . The novel compounds, 1, 2, and 3 

were synthesized under varying reaction conditions using ligands of different bulk. The compounds 1, 2, 

and 3 were all obtained as colorless crystals in the parent solvent upon storing in refrigerator at -30°C. 

The Al–H bonds in the compounds 1 and 2 were confirmed by measuring their IR spectra, which give 

characteristic peaks ranging between 1830 cm -1 to 1865 cm -1 . [1] The structures in solution of the 

compounds 1, 2, and 3 were determined by 1 H- and 13 C-NMR spectroscopy. MAS-NMR spectrum was 

recorded for compound 2 which is in good agreement to the solid state structure determined by single 

crystal X-rays analysis. The compounds were analyzed by single crystal X-rays diffraction and solid state 

structures were established for 1, 2, and 3. Compound 1 is pseudo pentamer while compound 2 is a two 

dimensional polymer. Here, it is important to note that the reactants and their stoichiometries were kept 

same during the synthesis of compounds 1 and 2. However, by varying the rate of dropping alcohol into 

the reaction mixture (3LiAlH4 + AlCl3) and the reaction time, two different compounds 1 and 2 were 

obtained. Compound 3 is dimer having central four-membered Al2O2 cyclic ring. The lower degree of 

polymerization in compound 3 is attributed to the bulky Clˉ ligand substituted for Hˉ and more sterically 

crowded 1-methylcyclohexoxy group. The elemental compositions of the compounds 1, 2, and 3 were 

determined using CHN analyzer for carbon and hydrogen. The experimentally determined carbon and 

hydrogen contents of the compounds 1, 2, and 3 were in good agreement to that calculated theoretically. 

The aluminum contents of the compounds 1, 2, and 3 were determined by complexometric titration 

method using EDTA as complexing agent while the chlorine in compound 3 was determined by titrimetry 

with AgNO3. [2-3] 

[1] M. Veith, S. Faber, H. Wolfanger and V. Huch, Chem. Ber., (1996), 129, 381. 

[2] Komplexometrische Bestimmungsmethoden mit Titriplex, Merck, 3. Auflage. 

[3] E. Gerdes, Qualitative Anorganische Analyse, Verlag Vieweg, 1995.


36 


Synthesis and Properties of Phosphole-Based Smart Molecular Materials 

Yi Ren and Thomas Baumgartner 

(thomas.baumgartner@ucalgary.ca) 

Department of Chemistry, University of Calgary, 2500 University Dr. NW, Calgary, AB T2N 1N4, 

Canada 

Phosphole-based π-conjugated compounds have recently attracted significant attention, due their unique 

electronic properties. [1] The materials have shown considerable potential for a variety of practical 

applications, such as organic light-emitting diodes, field-effect transistors, and solar cells. Equally 

desirable for practical applications are highly ordered bulk phases of the materials, and self-assembly 

features have been found to play an important role in the efficient charge-, ion-, and charge-transfer 

properties of organic electronics. 

This presentation will highlight our efforts in efficiently designing ring-fused phosphole building blocks 

that provide access to smart molecular materials. [2] Our multi-pronged approach addresses their intrinsic 

properties, such as electronics and photophysics, but also some extrinsic properties that have opened up a 

path to utilizing these functional building blocks in the generation of highly ordered nano/microstructures. 

[1] (a) M. G. Hobbs, T. Baumgartner, Eur. J. Inorg. Chem. 2007, 3611. (b) Y. Matano, H. Imahori, Org. 

Biomol. Chem. 2009, 7, 1258. 

[2] (a) Y. Ren, W. H. Kan, M. A. Henderson, P. G. Bomben, C. P. Berlinguette, V. Thangadurai, T. 

Baumgartner, J. Am. Chem. Soc. 2011, 133, 17014. (b) Y. Ren, W. H. Kan, V. Thangadurai, T. 

Baumgartner, Angew. Chem. Int. Ed. 2012, 51, 3964.

Oral 19 Tuesday 8:50 a.m. and Poster 65 

Phosphorus-Containing Copolymers for Suzuki Cross-Coupling 

37 


Tom H. H. Hsieh, Thomas W. Hey and Derek P. Gates 

(thsieh@chem.ubc.ca) 

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, 

V6T 1Z1, Canada 

Traditionally, monodentate and bidentate phosphines have comprised the majority of phosphoruscontaining 

ligands in catalysis. The use of hybrid inorganic/organic phosphorus-containing polymers have 

been largely unexplored. We have previously reported that copolymers formed from the addition 

polymerization of phosphaalkene and styrene are capable of supporting transition metal cross-coupling 

catalysis. [1] We now report the recent developments in the ease of purification, increased substrate and 

catalyst scope, and ability to recycle the poly(methylenephosphine)-polystyrene copolymer (PMP-PS). 

Furthermore, copolymer microstructure and modifications, such as crosslinking with divinylbenzene, will 

be presented. 

[1] Tsang, C.-W.; Baharloo, B.; Riendl, D.; Yam, M.; Gates, D.P. Angew. Chem. Int. Ed. 2004, 43, 5682.

Oral 20 Tuesday 8:50 a.m. 

Conjugated Boracycles: Electron-Deficient Ring Systems 

Pangkuan Chen, Jiawei Chen, Didier A. Murillo and Frieder Jäkle 

(fjaekle@rutgers.edu) 

Department of Chemistry, Rutgers University – Newark, Newark, NJ 07302\ 

38 


Electron-deficient organoboranes play important roles in various organic transformations, as activators of 

transition metal complexes in olefin polymerization, and in the activation of small molecules when 

combined with bulky Lewis bases (so-called frustrated Lewis pairs). The Lewis acidic properties are also 

exploited in the recognition of anions. Especially attractive are bidentate and polyfunctional species, 

which tend to exhibit the strongest affinities due to cooperative and/or chelate effects. Conjugated 

systems that feature multiple tricoordinate borane moieties, on the other hand, are attractive in optical and 

electronic applications (e.g. nonlinear optics, luminescent imaging materials, OLEDs, OFETs, 

photovoltaics), due to extension of conjugation via the empty p-orbital and the electron-acceptor effect of 

boranes. [1] 

In this presentation we will discuss our efforts toward conjugated cyclics in which multiple electrondeficient 

boranes interact with each other through π-conjugated organic or organometallic bridging 

groups. [2,3] Among these is the intriguing new class of boracyclophanes and related macrocycles that are 

highly electron-deficient, yet can be switched into electron-rich systems by anion coordination. [3] 

[1] W. E. Piers, G. J. Irvine, V. C. Williams, Eur. J. Inorg. Chem. 2000, 2131. F. Jäkle, “Boron: 

Organoboranes” in Encyclopedia of Inorganic Chemistry, 2 nd edition, Ed. B. King, Wiley-VCH, 

Weinheim, 2005; pp 560-598. D. W. Stephan, G. Erker, Angew. Chem., Int. Ed. 2009, 49, 46. C. R. 

Wade, A. E. J. Broomsgrove, S. Aldridge, F. P. Gabbai, Chem. Rev. 2010, 110, 3958. F. Jäkle, Chem. 

Rev. 2010, 110, 3985-4022 

[2] K. Venkatasubbaiah, T. Pakkirisamy, A. Doshi, R. A. Lalancette, F. Jäkle, Dalton Trans. 2008, 4507- 

4513; T. Pakkirisamy, K. Venkatasubbaiah, W. S. Kassel, A. L. Rheingold, F. Jäkle, 

Organometallics 2008, 27, 3056-3064; T. Pakkirisamy, J. Chen, R. A. Lalancette, F. Jäkle, 

Organometallics 2011, 33, 6734-6741; J. Chen, Didier A. Murillo, R. A. Lalancette, F. Jäkle, 

unpublished results. 

[3] P. Chen, R. A. Lalancette, F. Jäkle, J. Am. Chem. Soc. 2011, 133, 8802-8805; P. Chen, F. Jäkle, J. Am. 

Chem. Soc. 2011, 133, 20142-20145; P. Chen, R. A. Lalancette, F. Jäkle, 2012, submitted.


Synthesis and Properties of 1-Phospha-2-boraacenaphthene 

39 


Takahiro Sasamori, 1 Akihiro Tsurusaki, 1 Atsushi Wakamiya, 1,2 Kazuhiro Nagura, 2 Stephan Irle, 2 

Shigehiro Yamaguchi 2 and Norihiro Tokitoh 1 

(sasamori@boc.kuicr.kyoto-u.ac.jp) 

1 Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, JAPAN 

2 Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya 464- 

8602, Japan 

Combinations of group 13 and 15 elements have attracted much attention in recent years from the 

viewpoint of material science such as π-electron conjugated molecules. [1] In such series with both 

phosphorus and boron atoms, phosphaborine [2a] and phosphonium- and borate-bridged stilbene [2b] have 

been reported. On the other hand, we have recently reported the synthesis and properties of 1,2-dimesityl- 

1-phospha-2-boraacenaphthene (1), which is a unique heterocyclic compound bearing −B a bond P 

tethered with a naphthyl unit at the 1,8-positions. [3] We report here the synthesis and properties of the first 

stable 1-phospha-2-boraacenaphthene 1. 

Reduction of 1-dimesitylboryl-8-dichlorophosphinonaphthalene 2 with magnesium metal in THF at r.t. 

gave 1-phospha-2-boraacenaphthene 1 as orange crystals in 91% yield via the migration of the Mes group 

from the B atom to the P atom. The structure of 1 was characterized by the spectroscopic and X-ray 

crystallographic analyses. It is worth noting that 1 was found to be orange in color, both in the crystalline 

state and in solution, in contrast to the previously reported phosphinoboranes, which are colorless or 

yellow crystals. Furthermore, 1 exhibited weak but apparent orange emission in solution. The chemical 

and physical properties of 1 will be discussed in detail. 

[1] A. Fukazawa, S. Yamaguchi, Chem. Asian J. 2009, 4, 1386. 

[2] a) T. Agou, J. Kobayashi, T. Kawashima, Org. Lett. 2005, 7, 4373. b) A. Fukazawa, H. Yamada, S. 

Yamaguchi, Angew. Chem. Int. Ed. 2008, 47, 5582. 

[3] A. Tsurusaki, T. Sasamori, A. Wakamiya, S. Yamaguchi, K. Nagura, S. Irle, N. Tokitoh, Angew. 

Chem. Int. Ed. 2011, 50, 10940.


40 


Exploring Non-Covalent Interactions and Hypervalency: Reactions of 

Acenaphthene Chalcogen Compounds 

Fergus R. Knight, Rebecca A. M. Randall, Kasun S. Athukorala Arachchige, Lucy Wakefield, L. K. 

Aschenbach, D. B. Cordes, A. Baggott, John M. Griffin, Sharon E. Ashbrook, Michael Bühl, Alexandra 

M. Z. Slawin and J. Derek Woollins (frk@st-andrews.ac.uk) 

EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK 

The interaction of atoms is an integral aspect of chemistry, biology and materials science. Whilst there 

have been great advances in the knowledge of covalent and ionic bonding, ambiguity over “hypervalent” 

species still remains a topic of interest and a full understanding of non-covalent interactions has yet to be 

developed. When bulky heteroatoms are constrained in unavoidably congested environments, non-bonded 

interactions arise as a consequence of a direct overlap of orbitals. Such bonding situations can be 

accomplished by positioning members of Groups 16 and 17 at suitable locations in a rigid organic 

framework, for example naphthalene and related 1,2-dihydroacenaphthylene (acenaphthene). 

Acenaphthene compounds (Acenap[X][EPh] (Acenap = acenaphthene-5,6-diyl; X = Br, I; E = S, Se, Te) 

and Acenap[EPh][E`Ph] E/E` = S, Se, Te) experience a general increase in peri-separation for molecules 

accommodating heavier congeners and maps the trends observed previously for analogous naphthalene 

derivatives. [1,2] Nevertheless, conformation of the aromatic ring systems dominates the geometry of the 

peri-region, with the anomalies observed correlated to the ability of the frontier orbitals of the halogen or 

chalcogen atoms to take part in attractive or repulsive interactions. [1,2] The parent chalcogen compounds 

react with dibromine and diiodine acceptors to afford a group of structurally diverse addition products 

containing hypervalent three-body fragments; insertion adducts (X-R2Te-X) exhibiting molecular see-saw 

geometries, neutral charge-transfer (CT) spoke adducts (R2Se-I-I), bromoselanyl cations [R2Se-Br] + ···[Br- 

Br2] - . [3] Reaction with methyl triflate afforded a series of monocation chalconium salts containing quasilinear 

three-body CMe-E···Z (E = Te, Se, S; Z = Br/E) fragments, confirmed by DFT as the onset of threecenter, 

four-electron bonding. The increasingly large J values for Se-Se, Te-Se and Te-Te coupling 

observed in the 77 Se and 125 Te NMR spectra give further evidence for the existence of a weakly-attractive 

through-space interaction. [4] ‘Electrochemically informed synthesis’ led to the oxidation of ditellurium 

compound Acenap(TePh)2 with AgBF4 and AgOTf affording two dication salts. [5] Similar reactions with 

derivatives containing lighter members of Group 16 afforded a series of silver(I) coordination 

compounds, generating 3D metal-organic frameworks (MOFs), 1D polymeric chains and simple 

monomeric complexes. [6] 

[1] F. R. Knight, A. L. Fuller, M. Bühl, A. M. Z. Slawin and J. D. Woollins, Chem. Eur. J., 2010, 16, 

7503; F. R. Knight, A. L. Fuller, M. Bühl, A. M. Z. Slawin and J. D. Woollins, Chem. Eur. J., 2010, 16, 

7605. [2] L. K. Aschenbach, F. R. Knight, R. A. M. Randall, D. B. Cordes, A. Baggott, M. Bühl, A. M. 

Z. Slawin and J. D. Woollins, Dalton Trans., 2012, 41, 3141. [3] F. R. Knight, K. S. Athukorala 

Arachchige, R. A. M. Randall, M. Bühl, A. M. Z. Slawin and J. D. Woollins, Dalton Trans., 2012, 41, 

3154. [4] F. R. Knight, R. A. M. Randall, K. S. Athukorala Arachchige, L. Wakefield, J. M. Griffin, S. E. 

Ashbrook, M. Bühl, A. M. Z. Slawin and J. D. Woollins, 2012, J. Am. Chem. Soc., submitted. [5] R. T. 

Boeré, T. L. Roemmele, L. K. Aschenbach, R. A. M. Randall, F. R. Knight, M. Bühl, A. M. Z. Slawin 

and J. D. Woollins, unpublished work. [6] F. R. Knight, R. A. M. Randall, L. Wakefield, A. M. Z. Slawin 

and J. D. Woollins, Chem. Eur. J., submitted.


41 


Synthesis, Structures and Reactions of Stannylene-bridged Ru Complexes 

Derived from Tetraethyldilithiostannole 

Masaichi Saito, a Takuya Kuwabara, a Jing Dong Guo, b Shigeru Nagase b 

(masaichi@chem.saitama-u.ac.jp) 

a Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimookubo, 

Sakura-ku, Saitama-city, Saitama, 338-8570, Japan 

b Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho, Sakyou-ku, 

Kyoto, 606-8103, Japan 

Group 14 metallole anions and dianions have received considerable attention in terms of their aromaticity 

and their potential usefulness as ligands for transition metal complexes. [1] There have already been 

reported several transition metal complexes coordinated by metallole ligands in η 5 fashions, [2] which were 

synthesized by the reactions of monoanion equivalents of metalloles with transition metal reagents. In 

contrast, there are no reports on the reactions of dianion equivalents of metalloles with transition metal 

reagents. We therefore examined the reactions of dilithiotetraphenylstannole [3] with various transition 

metal reagents. However, no identifiable products were obtained. We next investigated the reactions of 

tetraethyldilithiostannole 1 [4] with [Cp*RuCl]4, and unexpected products were produced. 

After addition of diethyl ether to a mixture of tetraethyldilithiostannole 1 and [Cp*RuCl]4 (0.5 eq), 

bis(stannylene)-bridged dinuclear Ru complex 2 was isolated in 13% yield. To investigate the mechanism 

for the formation of 2, the reaction of 1 with 0.2 equivalent of [Cp*RuCl]4 was examined, and 

dilithiobis(stannylene)-bridged dinuclear Ru complex 3 was isolated in 80% yield. The nature of the 

Ru−Ru bonds in 2 was clarified by theoretical calculations. 

Et 

Et Li Et Et 

Et 

Et Et 

Sn 

Et 

Sn 

Et Et 

Ru 

Sn Et 

Li 

Ru 

Cp* 

Cp* Et 

1 2 

Li 

Cp* 

Et 

Et 

Ru 

Sn Sn 

Ru 

EtCp* Et 

Li 

[1] For example of recent reviews, see: (a) Saito, M.; Yoshioka, M. Coord. Chem. Rev. 2005, 249, 765. 

(b) Lee, V. Y.; Sekiguchi, A. Angew. Chem., Int. Ed. 2007, 46, 6596. (c) Lee, V. Y.; Sekiguchi, A. In 

Organometallic Compounds of Low-coordinate Si, Ge, Sn and Pb, Wiley, Chichester, p335. (d) 

Saito, M. Coord. Chem. Rev. 2012, 256, 627. 

[2] (a) Freeman, W. P.; Tilley, T. D.; Rheigold, A. L.; Ostrander, R. L. Angew. Chem., Int. Ed. Engl. 

1993, 32, 1744. (b) Freeman, W. P.; Tilley, T. D. J. Am. Chem. Soc. 1994, 116, 8428. (c) Dysard, J. 

M.; Tilley, T. D. J. Am. Chem. Soc. 1998, 120, 8245. (d) Dysard, J. M.; Tilley, T. D. J. Am. Chem. 

Soc. 2000, 122, 3097. (e) Freeman, W. P.; Dysard, J. M.; Tilley, T. D. Organometallics 2002, 21, 

1734. (f) Lee, V. Y.; Kato, R.; Sekiguchi, A.; Krapp, A.; Frenking, G. J. Am. Chem. Soc. 2007, 129, 

10340. (g) Yasuda, H.; Lee, V. Y.; Sekiguchi, A. J. Am. Chem. Soc. 2009, 131, 9902. 

[3] Saito, M.; Haga, R.; Yoshioka, M.; Ishimura, K.; Nagase, S. Angew. Chem., Int. Ed. 2005, 44, 6553. 

[4] Saito, M.; Kuwabara, T.; Kambayashi, C.; Yoshioka, M.; Ishimura, K. Nagase, S. Chem. Lett. 2010, 

39, 700. 

Et 

Et 

3 

Et 

Et


42 


Subsitution: Multiple Roles of a Ru=Pr2 Complex in P-C Bond Forming Reactions 

Krista M.E. Morrow, a Dimitrios A. Pantazis, b Robert McDonald, c Marc-André M. Hoyle, Sophie Langis- 

Barsetti, a Roman Belli, a Lisa Rosenberg 

a Department of Chemistry, University of Victoria, Victoria, Canada. b Max Plank Institute for Bioinorganic 

Chemistry, Mülheim an der Ruhr, Germany. c X-ray Crystallography Laboratory, University of Alberta, 

Edmonton, Canada. E-mail:lisarose@uvic.ca 

Homogeneously catalyzed stereoselective hydrophosphination of alkenes and alkynes can allow the 

synthesis of enantiomerically pure chiral phosphines, but this atom-economic process remains underdeveloped 

relative to analogous hydroamination reactions. Terminal phosphido complexes have been 

identified as important intermediates in the hydrophosphination of simple alkenes and alkenes mediated by 

early-metal catalysts, and of activated, Michael-type substrates mediated by late-metal catalysts. We have 

prepared a ruthenium phosphido complex containing a Ru=PR2 double bond that undergoes [2+2] 

cycloaddition reactions with both simple and activated alkenes[1] and alkynes[2]. Our kinetic and 

computational studies point to kinetic rather than thermodynamic control of diastereomer ratios in the 

product metallacycles, and a change in rate-determining step for the cycloaddition of electron-poor, relative 

to electron-rich, unsaturated substrates. For the former, nucleophilicity of the phosphido ligand is critical, 

for the latter, the Ru-P double bond character plays a major role. This presentation will describe our 

mechanistic studies of these reactions and our recent efforts to extend these critical P-C bond-forming steps 

to a full hydrophosphination catalytic cycle. 

[1] E. J. Derrah, D.A. Pantazis, R. McDonald, L. Rosenberg, Angew. Chem. Int. Ed. 2010, 49, 3367. [2] E. 

J. Derrah, R. McDonald, L. Rosenberg, Chem. Commun., 2010, 46, 4592. 

Withdrawn: N-alkylpyridine and Oxobenzene Bridged Bis-dithiazolyls, by A. 

Mailman, X. Yu, K. Lekin, S. M. Winter, J. Wong, A. R. Balo, R. Roberts and R. T. Oakley 

(amailman@uwaterloo.ca), Department of Chemistry, University of Waterloo, Canada


43 


Exploring the Free Radical Reactivity of Cyclic Silylenes, Germylenes and 

Silenes using Muon Spin Spectroscopy 

Robert West, a Amitabha Mitra, a Paul Percival b,c and Jean-Claude Brodovitch b,c 

(west@chem.wisc.edu) 

a Organosilicon Research Center, University of Wisconsin, Madison WI 53706 USA 

b Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A 1S6, Canada 

c TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3, Canada 

The TRIUMF cyclotron facility in Vancouver BC is one of only four sites in the world capable of 

providing intense beams of spin-polarized positive muons suitable for muon spin resonance spectroscopy 

(µSR). [1,2] Positive muons are particles of antimatter, resembling protons but with mass about 1/9 of a 

proton. They have a lifetime of only 2.2 µs, decaying into positrons. Muons capture an electron to form 

muonium atoms, which can add to unsaturated molecules much like H atoms. The sample is placed in a 

magnetic field transverse to the muon spin polarization, so that the muon spins precess in similar manner 

to nuclei in NMR and electrons in ESR. The precession frequencies, which constitute the µSR spectrum, 

are derived from the time dependence of the angular distribution of positrons emitted on muon decay. 

The muon hyperfine splitting constant for a muoniated radical is readily obtained from frequency splitting 

in the µSR spectrum; this constant is a measure of the interaction between the muon and the unpaired 

electron, and provides structural and bonding information. 

We have studied the µSR spectra of free radicals formed by muonium addition to several cyclic silylenes, 

germylenes and silenes. [2,3] The results provide much information about the free-radical chemistry of 

cyclic silylenes and silenes, as well as new discoveries about the behavior of muon-containing molecules. 

[1] McKenzie, I.; Roduner, E., Using polarized muons as ultrasensitive spin labels in free radical 

chemistry, Naturwissenschaften, 2009, 96, 873-887. 

[2] West, R.; Percival, P. W., Organosilicon Compounds Meet Suabtomic Physics: Muon Spin 

Resonance, Dalton Trans., 2010, 39, 9209-9216. 

[3] McCollum, B. M.; Brodovitch, J.-C.; Clyburne, J. A. C.; Percival, P. W.; Tomasik, A. C.; West, R., 

Reaction of Stable N-heterocyclic Silylenes and Germylenes with Muonium, Chem.- Eur. J., 2009, 

15, 8409-8412.


Synthesis and Properties of Stannabenzenes 

44 


Norihiro Tokitoh, Yoshiyuki Mizuhata and Naoya Noda 

(tokitoh@boc.kuicr.kyoto-u.ac.jp) 

Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan 

Aromatic hydrocarbons such as benzene and naphthalene are among the most fundamental class of 

organic compounds and play very important roles in organic chemistry. We have already succeeded in 

the synthesis and isolation of the first stable examples for neutral sila- and germaaromatic compounds 

(e.g. compounds 1 and 2) by taking advantage of kinetic stabilization afforded by an efficient steric 

protection group, Tbt and Bbt. [1] In view of the recent progress in the chemistry of sila- and 

germaaromatic compounds, the synthesis of stannaaromatic compounds is of great interest from the 

standpoint of systematic elucidation of the properties of metallaaromatic systems of heavier group 14 

elements. Recently, we have succeeded in the synthesis and isolation of 2-stannanaphthalene 3 as a stable 

compound and revealed its high aromaticity. [2] However, neutral stannaaromatic compounds are still 

elusive and their properties have not been disclosed yet so far. We report here the synthesis of 

stannabenzenes 4 having a more fundamental stannaaromatic skeleton. 

Generation of stannabenzenes 4 was examined by the reaction of bulky bromostannanes 5 with lithium 

diisopropylamide in hexane at –40 °C. In the cases using 5a-c as a precursor, only [4 + 2] dimers 6a-c 

were observed at room temperature, indicating the generation of the corresponding stannabenzenes 4ac. 

[3] Thus, the thermal stability 

of 4a and 4b was completely 

different from that of the sila- 

and germabenzenes bearing the 

same substituent. In the case 

using 5d as a precursor, on the 

other hand, NMR analysis of the reaction 

products at room temperature showed the 

co-existence of monomeric stannabenzene 

4d together with the corresponding dimer 

6d. The properties of stannabenzene 4d 

will be described along with an attempt at 

introducing an additional substituent to the 

stannabenzene ring. 

[1] Tokitoh, N. Acc. Chem. Res. 2004, 

37, 86. 

[2] a) Mizuhata, Y.; Sasamori, T.; Takeda, N.; Tokitoh, N. J. Am. Chem. Soc. 2006, 128, 1050. b) 

Mizuhata, Y.; Sasamori, T.; Nagahora, N.; Watanabe, Y.; Furukawa, Y.; Tokitoh, N. Dalton Trans. 

2008, 4409. 

[3] Mizuhata, Y.; Noda, N.; Tokitoh, N. Organometallics 2010, 29, 4781.


45 


Free Radicals formed by H Atom Addition to Cyclic Carbenes, Silylenes and 

Germylenes 

Paul Percival, a,b Graeme Langille, a Iain McKenzie a,b and Robert West c 

(percival@sfu.ca) 

a Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A 1S6, Canada 

b TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3, Canada 

c Organosilicon Research Center, University of Wisconsin, Madison WI 53706 USA 

Over the past few years we have studied the free radicals formed by H atom addition to carbenes, 

silylenes and germylenes. Our experimental method employs the exotic atom muonium, which is 

effectively a light isotope of hydrogen [1] . Muoniated radicals can be characterized by muon spin 

spectroscopy: muon spin rotation (µSR) to determine the muon hyperfine constant (hfc), and muon 

avoided level-crossing resonance (µLCR) to determine the hyperfine constants of other magnetic nuclei in 

the radical. We apply these techniques at the TRIUMF cyclotron facility, in Vancouver, the only site in the 

Americas with the necessary intense beams of spin-polarized muons. Our original focus was on radicals 

formed by H(Mu) addition to N-heterocyclic (NHC) ylidenes, as indicated below. However, we could not 

reconcile the muon hfcs of the radicals formed from silylenes with the predictions of quantum 

calculations. Part of the explanation lies in a coupling of the primary radical with a second silylene, so 

that a disilanyl product radical is observed [2] . This was confirmed in subsequent experiments on a series 

of NHC silylenes with different substituents on the nitrogens. The largest (diisopropylphenyl) served to 

slow the silyl coupling reaction so that we were able to detect the primary silyl radical, as evident from 

the muon hfc (931 MHz) [3] . The muon hfc in the primary silyl radical is much higher than for equivalent 

NHC alkyl (262 MHz, R = t-butyl) and germyl (650 MHz, R = t-butyl) radicals. The reasons for the nonintuitive 

order of hfcs will be discussed in terms of radical structure and dynamics. In particular, the 

lowest frequency vibrations are key to understanding the temperature dependence of the hfcs and the 

isotope effect on the muon/proton hfcs. 

[1] R. West and P.W. Percival, Dalton Trans. 39, 9209-9216 (2010). 

[2] B.M. McCollum, J.-C. Brodovitch, J.A.C. Clyburne, P.W. Percival, A. Tomasik, R. West, Chem. Eur. 

J. 15, 8409-8412 (2009). 

[3] A. Mitra, J.-C. Brodovitch, C. Krempner, P.W. Percival, P. Vyas and R. West, Angew. Chem. Int. Ed. 

49, 2893-2895 (2010).


46 


New Homopolyatomic Sulfur Cations Stabilized by Halogenated Boron 

Clusters 

Carsten Knapp, 

Janis Derendorf, Mathias Keßler and Christoph Bolli 

(cknapp@uni-wuppertal.de) 

Fachbereich C – Anorganische Chemie, Bergische Universität Wuppertal, Gaußstr. 20, 42119 

Wuppertal, Germany 

Perhalogenated closo-dodecaborate anions [B12X12] 2- (X = F, Cl, Br, I) are valuable weakly coordinating 

dianions for the stabilization of unusual cations and dications. [1] Improved syntheses for the 

perchlorinated dodecaborate [B12Cl12] 2- were reported, which now make this anion available on a large 

scale. [2,3] The first solid diprotic super acid H2B12Cl12, [4] the strong methylating agent Me2B12Cl12, [5] and 

the silylium compounds (R3Si)2B12Cl12 [6] are useful reagents. Oxidation of [B12Cl12] 2- leads to the radical 

anion [B12X12] •- and neutral B12Cl12, both being strong oxidizing agents themselves. [7] 

Combining the [B12Cl12] 2- anion with iodine and sulfur homopolyatomic cations followed by 

crystallization from supercritical sulfur dioxide lead to the isolation of salts containing the [I3] + cation and 

the novel [S20] 2+ and [S8] + cations. The dication [S20] 2+ has a structure similar to that of the known [S19] 2+ 

and consists of two seven-membered sulfur rings bridged by a six-membered sulfur chain. The [S8] + 

structure is similar that of [S8] 2+ but contains a significantly longer transannular sulfur-sulfur contact. 

[1] C. Knapp, Comprehensive Inorganic Chemistry II 2012, in press. 

[2] V. Geis, K. Guttsche, C. Knapp, H. Scherer, R. Uzun, Dalton Trans. 2009, 2687. 

[3] W. Gu, O, V. Ozerov, Inorg. Chem. 2011, 50, 2726. 

[4] A. Avelar, F. S. Tham, C. A. Reed, Angew. Chem. Int. Ed. 2009, 48, 3491. 

[5] C. Bolli, J. Derendorf , M. Keßler, C. Knapp, H. Scherer, C. Schulz, J. Warneke, Angew. Chem. Int. 

Ed. 2010, 49, 3536. 

[6] M Keßler, C. Knapp, V. Sagawe, H. Scherer, R. Uzun, Inorg. Chem. 2010, 49, 5223. 

[7] R. T. Boeré, S. Kacprzak, M. Keßler, C. Knapp, R. Riebau, S. Riedel, T. L. Roemmele, M. Rühle, H. 

Scherer, S. Weber, Angew. Chem. Int. Ed. 2011, 50, 549.


Polycyclic π-Electron System with Boron at its Center 

47 


Shohei Saito, 

Kyohei Matsuo and Shigehiro Yamaguchi 

(s_saito@chem.nagoya-u.ac.jp.com) 

Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan 

We disclose a new planarized triarylborane in which the tricoordinated 

boron atom is embedded in a fully fused polycyclic 

π-conjugated skeleton. [1] The compound 1 shows high stability 

toward oxygen, water, and silica gel, despite the absence of 

steric protection around the boron atom. Reflecting the electrondonating 

character of the π-skeleton and the electron-accepting 

character of the boron atom, this compound shows broad 

absorption bands that cover the entire visible region and a 

fluorescence in the visible/near-IR region. In addition, this 

compound shows dramatic property changes upon formation of a tetracoordinated borate, such as 

thermochromic behavior in the presence of pyridine. Further studies on the application of this 

boron π-system as well as the controlled synthesis of Boron-Doped Nanographene are currently 

underway in our laboratory. 

[1] Saito, S.; Matsuo, K.; Yamaguchi, S. J. Am. Chem. Soc. 2012, 134, 9130. (highlighted in 

Spotlights)


48 


Donor-Acceptor Stabilization of Unusual Low Oxidation State Main Group 

Species: Placing Chemical Genies in a Bottle 

Eric Rivard, Ibrahim Al-Rafia, Adam Malcolm, Michael Ferguson and Robert McDonald 

(erivard@ualberta.ca) 

Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, AB, T6G 2G2, 

Canada 

This talk will address the use of a general donor-acceptor protocol for the isolation of unusual main group 

hydrides, such as SiH2, GeH2 and SnH2 and the ethylene analogues H2SiEH2 (E = Ge and Sn) at ambient 

temperature. [1] In addition, we will detail our attempts to access stable complexes of unsaturated main 

group species such as BN and PN. [2] 

[1] (a) Thimer, K.; Al-Rafia, S. M. I.; Ferguson, M. J.; McDonald R.; Rivard, E. Chem. Commun. 2009, 

7119. (b) Al-Rafia, S. M. I.; Malcolm, A. C.; Liew, S. K.; Ferguson, M. J.; Rivard, E. J. Am. Chem. 

Soc. 2011, 133, 777. (c) Al-Rafia, S. M. I.; Malcolm, A. C.; Liew, S. K.; Ferguson, M. J.; McDonald 

R.; Rivard, E. Chem. Commun. 2011, 6987. (d) Al-Rafia, S. M. I.; Malcolm, A. C.; McDonald R.; 

Ferguson, M. J.; Rivard, E. Angew. Chem., Int . Ed. 2011, 50, 8354. (e) Al-Rafia, S. M. I.; Malcolm, 

A. C,; McDonald R.; Ferguson, M. J.; Rivard, E. Chem. Commun. 2012, 1308. 

[2] Al-Rafia, S. M. I.; Ferguson, M. J.; Rivard, E. Inorg. Chem. 2011, 50, 10543.


Cu24 Rhombicuboctahedral Clusters with Oh Symmetry 

Chen-Wei Liu 

(chenwei@mail.ndhu.edu.tw) 

Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401 

49 


While the geometry of rhombicuboctahedron, an Archimedean polyhedron composed of eighteen square 

faces and eight triangular faces (83 + 64 + 124), has been observed in metal organic polyhedral network 

structures, discrete metal clusters having this sort of ascetically pleasing structure, to the best of our 

knowledge, have never been identified. Herein we report the first Cu24 rhombicuboctahedral cluster 

formulated as [Cu24(S8)(H)15(S2CNR2)12] + with Oh symmetry, a reduction product of hydrido copper 

clusters with borohydrides. 

Molecules of the type, [Cu8(µ4-H)(dtc)6] + , having a hydride-centered, tetracapped tetrahedral copper 

cluster topology, can be further reduced to yield Cu24 rhombicuboctahedral clusters. Their composition is 

primarily determined by ESI mass spectrometry and conformation by single crystal X-ray diffraction 

analysis. These highly symmetric molecules display an onion-type structure which consists of an 

idealized rhombicuboctahedral Cu24 core that is further surrounded by a truncated octahedral polyhedron 

consisting of twenty-four sulfur atoms from twelve dithiocarbamate (dtc) ligands. In addition, a catenated 

sulphur cage whose eight S atoms disorder dynamically at twelve positions of a cuboctahedron is trapped 

inside the Cu24 capsule. Finally neutron diffraction analysis clearly suggests there are eight threecoordinate 

(µ3-H) hydrides and six four-coordinate hydrides (µ4-H), which capped the eight triangular 

faces (83) and six square faces (64) of a rhombicuboctahedron, respectively.


50 


Dithienylethenes Containing Diazabutadiene Functionality and their Main 

Group Derivatives 

Jacquelyn T. Price and Paul J. Ragogna 

(jprice6@uwo.ca pragogna@uwo.ca) 

Department of Chemistry and the Center for Materials and Biomaterials Research 

Western University, 1151 Richmond St, London, Ontario, N6A 5B7, Canada 

Within the past decade photochromic materials have received a large amount of interest because of their 

ability to function as potential photoswitchable molecular devices and optical memory storage systems. [1] 

Among these materials, diaryethenes have proven to have the greatest potential in this field because of 

their excellent fatigue resistance and thermal irreversibility. [2] There have been extensive studies focused 

on these systems containing mostly organic frameworks and only recently the coordination of these 

systems to transition metal centers, which enhance the stability of the photochromic system and modulate 

the photochromic reactivity has been explored. [3] While diazabutadiene ligands are well known for their 

ability to be redox active ligands, bind to transition metals [4] and support low valent, low oxidation state 

main group elements [5,6] there has been no report on the functionalization of this ligand type with 

diarylethenes. We have synthesized a new class of diazabutadiene ligands with photochromic thiophene 

rings in the backbone and have synthesized the borane and phosphine complexes. Their synthesis and 

ability to undergo reversible photochromic ring closing and opening reactions will be discussed. 

[1] Feringa, B. L., Ed. Molecular Switches; Wiley-VCH: Weinheim, Germany, 1990. [2] Irie, 

M. Chemical Reviews 2000, 100, 1685-1716. [3] Hasegawa, Y.; Nakagawa, T.; Kawai, T. 

Coordination Chemistry Reviews, 254, 2643-2651. [4] Van, K. G.; Vrieze, K. Adv. Organomet. 

Chem. 1982, 21, 151-239. [5] Gudat, D. Accounts of Chemical Research 2010, 43, 1307-1316. 

[6] Asay, M.; Jones, C.; Driess, M. Chemical Reviews 2011, 111, 354-396.


51 


Large Effect of Subtle Building Defects on the Physical Properties of 2D 

Boron Layered “Tiling” Compounds 

1-3 1 4 4 5 

Takao Mori , Ievgen Kuzmych-Ianchuk , Kunio Yubuta , Toetsu Shishido , Shigeru Okada , Kunio 

Kudou 

( 

6 , Yurii Prots 7 and Yuri Grin 7 

mori.takao@nims.go.jp) 

1 

National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, 305-0044 Japan 

2 

Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, 739-8514 Japan 

3 

University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 Japan 

4 

Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 Japan 

5 

Kokushikan University, 4-28-1 Setagaya, Tokyo, 154-8515 Japan 

6 

Kanagawa University, 3-27-1 Rokkakubashi, Yokohama, 221-8686 Japan 

7 

Max Planck Institute Chemical Physics of Solids, Nothnitzer Str. 40, 01187 Dresden, Germany 

Rare earth borides have yielded intriguing systems for f-electron physics and chemistry [1] . We have taken 

a systematic approach to the AlB2-type analogous “tiling” compounds, composed of 2D boron atomic 

sheets (based on hexagonal graphitic structure) sandwiching rare-earth (R) and transition metal (Tr) atoms 

(Fig. 1). By selecting unexplored combinations of metal constituents, synthesis of myriad new 

compounds of these structure types can be envisioned. [2] REAlB4 in particular has attracted attention with 

recent discoveries, such as frustrated magnetism in α-HoAlB4 and ErAlB4, [3] and multiple magnetic 

anomalies in α-TmAlB4 below the Neel temperature indicated to be due to building defects. [4] The two 

main structure types of REAlB4; α- and β- , simply differ in their in-plane “tiling” arrangement of [5] and 

[7] B rings. Tm2AlB6 with [5], [6], [7] B rings was also successfully synthesized and a magnetic field 

induced state with extreme stability versus field observed. [2] With a counterintuitive approach to crystal 

growth, single crystals of α-TmAlB4 were successfully grown, which were indicated from TEM and 

advanced XRD analysis to be virtually free from 

the ubiquitous building defects. The physical 

properties show a striking difference from those 

of conventional α-TmAlB4 crystals, and the large 

effect of the building defects on the physical 

properties could be directly confirmed, such as the 

origin of “missing entropy” [5]. These building 

defects are quite subtle and may in some cases be 

unperceived, and might possibly be the origin of 

anomalous behavior in other layered systems also. 

Fig. 1 AlB 2 -type analogous “tiling” compounds 

[1] e.g. T. Mori, in: Handbook on the Physics and Chemistry of Rare Earths, Vol. 38, North-Holland, 

Amsterdam, 2008 p. 105-173. 

[2] T. Mori, T. Shishido, K. Nakajima, K. Kieffer, and K. Siemensmeyer, J. Appl. Phys. 105, 07E124 

(2009), T. Mori, in: The Rare Earth Elements: Fundamentals and Application, J. Wiley & Sons, New 

York, in press (2012). 

[3] T. Mori, J. Appl. Phys. 109, 07E111 (2011). 

[4] T. Mori, H. Borrmann, S. Okada, K. Kudou, A. Leithe-Jasper, U. Burkhardt, Yu. Grin, Phys. Rev. B 

76, 064404 (2007). 

[5] T. Mori, I. Kuzmych-Ianchuk, K. Yubuta, T. Shishido, S. Okada, K. Kudou, Yu. Grin, J. Appl. Phys. 

111 07E127 (2012).


New Oxyanions of Sulfur 

52 


S. Greer, F. Grein, F. Leblanc, A. Mailman, B.Müller, J. Passmore, T. A. P. Paulose, M. Rautiainen and 

S. Richardson 

(passmore@unb.ca) 

Department of Chemistry, University of New Brunswick, Fredericton, NB, E3B 5A3, Canada 

The binary oxyanions of sulfur were mostly prepared at least 100 years ago and are part of the backbone 

of basic chemistry of the elements and are of industrial importance. However we estimated that the 

energetics of reaction of sulfate and dithionite salts with SO2 become increasingly favorable as the size of 

the cation increases as shown in figure 1 leading to two new classes of oxyanions, the polythionites, 

(SO2)n 2- and the mixed S(VI) and S(IV) oxyanions, O3SO(SO2)n 2- . This also provides a new way to 

reversibly sequester SO2 an atmospheric pollutant. Our experimental results will be presented.


Bis[N,N´-diisopropylbenzamidinato(–)]silicon(II): 

A Novel Donor-Stabilized Silicon(II) Species 

53 


R. Tacke, 

K. Junold, J. A. Baus, C. Burschka 

(r.tacke@uni-wuerzburg.de) 

Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, D-97074 Würzburg, Germany 

Starting from the six-coordinate bis(amidinato)silicon(IV) complex 1, the novel three-coordinate 

bis(amidinato)silicon(II) compound 4 was synthesized by reductive HCl elimination. The donor-stabilized 

silylene 4 reacts with W(CO)6 as a nucleophile to give the five-coordinate silicon(II) compound 5. 

Treatment of 4 with I2, PhSe–SePh, N2O, S8, Se, or Te results in an oxidative addition to give the five- (6– 

9) and six-coordinate (2, 3) bis(amidinato)silicon(IV) complexes 2, 3, and 6–9. The studies reported here 

were performed in context with our systematic investigations on higher-coordinate silicon compounds 

(for recent publications, see refs. [1–4]). 

Molecular structures of 4 (left), 5 (middle), and 7 (right) in the crystal. 

[1] K. Junold, C. Burschka, R. Tacke, Eur. J. Inorg. Chem. 2012, 189–193. 

[2] C. Kobelt, C. Burschka, R. Bertermann, C. Fonseca Guerra, F. M. Bickelhaupt, R. Tacke, Dalton 

Trans. 2012, 41, 2148–2162. 

[3] B. Theis, J. Weiß, W. P. Lippert, R. Bertermann, C. Burschka, R. Tacke, Chem. Eur. J. 2012, 18, 

2202–2206. 

[4] K. Junold, J. A. Baus, C. Burschka, R. Tacke, DOI: 10.1002/ange.201203109; Angew. Chem. Int. Ed. 

2012, DOI: 10.1002/anie.201203109.


A Crystalline Room Temperature-stable Singlet Nitrene 

54 


Fabian Dielmann, Olivier Back, Martin Henry-Ellinger and Guy Bertrand 

(fabian.d@gmx.de) 

Department of Chemistry, University of California, Riverside, Riverside, CA 92521-0403, USA 

More than two decades after the discovery of the first stable carbene, [1] we report the isolation and full 

characterization of a nitrogen analogue, namely a nitrene. [2] The bonding situation is reminiscent to that of 

metallonitrenes (nitrido metal complexes), which have extensively been studied due to their implications 

in biological nitrogen fixation by the nitrogenase enzymes, and the industrial Haber-Bosch hydrogenation 

process of converting N2 into NH3. The reactivity of this novel compound will be discussed, e.g. we 

demonstrate that the nitrene can activate P4 and is capable of complete nitrogen atom transfer to an 

organic fragment. 

[1] A. Igau, H. Grützmacher, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 1988, 110, 6463; A. Igau, A. 

Baceiredo, G. Trinquier, G. Bertrand, Angew. Chem. Int. Ed. Engl. 1989, 28, 621-622. 

[2] F. Dielmann, O. Back, M. Henry-Ellinger, P. Jerabek, G. Frenking, G. Bertrand, Science (submitted).

B1–B2 = 159.2(5) pm 

B1–B2 = 144.9(3) pm 

55 


Single, Double, Triple, Chains: New Forays into Boron-Boron-Bond 

Formation 

Holger Braunschweig 

(holger.braunschweig@uni-wuerzburg.de) 

Institute of Inorganic Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany 

Due to its inherent electron deficiency, boron prefers non-classical bonding regimes when combined to 

molecules with itself - in other words, boron forms polyhedral boranes, made up of multicenter bonds, 

rather than chains or rings with electron-precise boron-boron bonds. In the case of the latter, only very 

few well-defined examples have been published over the past decades, which all suffer from lowyielding, 

non-selective syntheses that solely rely on reductive coupling of amino(halo)boranes. 

Consequently, the area of classical boron-boron multiple bonds is relatively undeveloped. Over the past 

two years we have put significant effort into the development of new synthetic strategies to overcome this 

seemingly element-specific deficiency. Here, initial results on the following topics will be presented: 

metal-mediated dehydrocoupling of boranes [1] 

O 

catalyst 

O O 

B H 

B B 

O 

– H2 O O 

e.g. 0.05 mol% Pt (20 h); 11600 TON B2pin2 

improved reduction protocols for NHC-stabilized diborenes 

and diborynes [2] 

metal-promoted catenation of borylenes [3] 

Plenary 3 Tuesday 1:40 p.m. 

O 

O 

= 

cat 

O 

O , 

[1] Angew. Chem. Int. Ed. 2011, 50, 12613; Eur. Patent EP 11176448.6, 2011, submitted; Chem. Eur. J. 

2012, in press. 

[2] Science, 2012, in press. 

[3] Nature Chemistry, 2012, in press; Angew. Chem. Int. Ed. 2012, 51, in press. 

Me Me 

O 

Me Me O 

pin 

λmax = 599 

iPr 

iPr 

iPr 

N iPr 

B B 

N iPr 

iPr 

N 

N 

iPr 

iPr

Keynote 4 Tuesday 2:20 p.m. 

56 


Synthetic Investigations involving Unsaturated Phosphorus Intermediates 

Alexandra Velian, Daniel Tofan, Lee-Ping Wang and Christopher C. Cummins 

(ccummins@mit.edu) 

Department of Chemistry, Massachusetts Institute of Technology, USA 

Ultraviolet irradiation of P4 in the presence of 2,3-dimethylbutadiene (dmb) affords bicyclic 

organophosphorus ring systems containing a diphosphane P—P bond at the [4.4.0] ring fusion. 

Multireference CASSCF(4,9)-RSPT3 calculations have been carried out to investigate the P4 excited state 

potential energy surface; these theoretical studies have uncovered a direct dissociation pathway for 

conversion of P4 into two P2 molecules, making P2 a plausible intermediate in the observed reaction with 

2,3-dimethylbutadiene. New synthetic investigations stemming from the P2 double Diels-Alder adduct 

with dmb will be described, including single and double oxidation, reactions with sulfur-atom sources, 

and organic azide reactions. The latter have provided new bis-iminophosphane molecules suited to serve 

as transition-metal ligands by virtue of pre-organization. Studies of a nickel complex will be presented. In 

addition, bicyclo[2.2.2] group 10 complexes of the type L2M2P2(dmb)6 (see Figure; M = Ni, Pd, and Pt) 

will be discussed in terms of their self-assembly and ligand exchange reactions of the axial ligands L, 

where L = PPh3, AsPh3, SbPh3, CN(2,6-xylyl) etc.

Keynote 5 Tuesday 2:50 p.m. 

57 


The Influence of Donors on the Reactivity of Group 14 (Di)metallenes 

Kim M. Baines 

(kbaines2@uwo.ca) 

Department of Chemistry, Western University, London, Ontario, N6A 5B7, Canada 

One of the most important advances in inorganic chemistry over the last 30 years was the discovery of 

stable (at rt under an inert atmosphere) multiply bonded species of the heavier main group elements. The 

spectroscopic and structural characterization of these unsaturated species has profoundly influenced our 

understanding of structure, bonding and reactivity. [1] Multiply bonded compounds of the heavier main 

group elements have also proven to be powerful building blocks in organometallic/inorganic synthesis 

just as alkenes and alkynes are in organic synthesis. An impressive array of previously inaccessible 

compounds, particularly ring systems, has been made from (di)metallenes(ynes) (referring to metallenes 

[2] 

(M=C), dimetallenes (M=M) and dimetallynes ≡M)). (M Even more exciting are the innovative 

applications of this chemistry that are now being explored. Some addition reactions of distannynes 

(RSn≡SnR) have been found to be reversible suggesting that the use of multiply bonded compounds in 

catalysis is now in the realm of possibility. [3] Other intriguing examples include the exploitation of the 

highly regiospecific cycloaddition reactions of silenes (R2Si=CR2) in organic synthesis, [4] the addition 

polymerization of silenes, [5] germenes (R2Ge=CR2) [6] and phosphaalkenes (RP=CR2) [7] to give novel 

inorganic materials. 

To achieve the full potential of unsaturated heavier main group compounds, it is critical to have a broad 

understanding of their reactivity. Although it has long been recognized that polarized silenes and 

germenes form complexes with donors, over the past few years, we have noted a few striking examples of 

how a complexed donor can dramatically influence the reaction pathway of a (di)metallene. In this 

presentation, the influence of donors on the reactivity of (di)metallenes will be discussed. 

[1] For authoritative reviews see: Power et al. Chem. Rev. 2010 110, 3877; Robinson et al. Chem. 

Commun. 2009 5201. 

[2] Numerous reviews have been published: Si: Weidenbruch in “Chem of Organic Si Cmpds” (Eds 

Rappoport, Apeloig) Wiley, 3 (2001) 391; Kira J. Organomet. Chem. 2004 689, 4475; Mueller et al. 

in “Chem of Organic Si Cmpds” (Eds Rappoport, Apeloig) Wiley, 2 (1998) 857. Ge: Tokitoh et al. in 

“Chem of Organic Ge, Sn and Pb Cmpds” (Eds Rappoport, Apeloig) Wiley, 2 (2002) 843; 

Weidenbruch, Organomet. 2003 22, 4348 P: Dillon et al. “P: the carbon copy” Wiley 1998. 

[3] Power Nature 2010 263, 171. 

[4] Ottosson et al. Chem. Eur. J. 2006 12, 1576. 

[5] Baines et al. Chem. Mat. 2008 20, 5948. 

[6] Baines et al. Chem. Commun. 2008 2346. 

[7] Gates et al. Dalton Trans. 2010 39, 3151.

58 


The Effect of Base-coordination to the Si=Si Double Bonds of Cyclotrisilenes 

Michael J. Cowley, a Anukul Jana, a Kinga Leszczyńska, b Kai Abersfelder, a Peter Jutzi, b 

and David Scheschkewitz a 

(scheschkewitz@mx.uni-saarland.de) 

a Krupp-Chair of General and Inorganic Chemistry, Saarland University, D-66125 Saarbrücken, 

Germany 

b Faculty of Chemistry, University of Bielefeld, D-33613 Bielefeld, Germany, 

Unsaturated compounds with heavier main group elements have received considerable attention in the last 

few decades. Recently, low-coordinate main-group compounds have been likened to transition metals 

because of their vacant coordination site. [1] Such similarities raise the possibility of main group systems 

filling roles previously taken by transition metal compounds, for example in applications such as 

homogeneous catalysis. For this reason, main-group compounds displaying typical transition-metal type 

behaviour are of great interest. We will discuss recent results arising from our investigations into the 

reactivity of cyclotrisilenes and related germanium-containing compounds with Lewis bases. 

For example, N-heterocyclic carbene 2 binds reversibly to cyclotrisilene 1, forming the NHCcyclotrisilene 

adduct 3, which constitutes the first example of reversible base coordination to a Si-Si 

double bond. Compound 3 can be considered an experimental example of the charge separated resonance 

structures frequently used in bonding models of heavier main group multiple bonds. Furthermore, the 

reversibility of the NHC coordination of 1 by 2 evokes reversible ligand coordination at transition metal 

centres, a prerequisite for catalytic activity in such systems. 

[1] Power, P. P. Nature. 2010, 463, 171-177. 

Keynote 6 Tuesday 3:40 p.m.

Plenary 4 Tuesday 4:10 p.m. 

59 


Reactions of Small Molecules with Main Group Compounds Under Ambient 

Conditions 

Philip P. Power 

(pppower@ucdavis.edu) 

Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616 USA 

The lecture will summarize the work of the author and his group in the title area beginning with their 

discovery of the reaction of hydrogen with a digermyne in 2005. Recent work involving the addition and 

insertion reactions of cyclic and acyclic olefins with group 13 and group 14 unsaturated, multiple bonded 

species and the observation of C-H bond activation will also be a major theme of the presentation.

Oral 37 Tuesday 4:50 p.m. 

60 


Ge12{FeCp(CO)2}8[FeCpCO]: A Metalloid Germanium Cluster on the Way to 

an α-Polonium Structure of Germanium 

A. Schnepf and C. Schenk 

andreas.schnepf@uni-due.de 

Institute of Inorganic Chemistry, University Duisburg-Essen, Universitätsstrasse 5-7, 45117 Essen, 

Germany 

Starting from Ge(I) halides, we have been able to establish a fruitful synthetic route to metalloid cluster 

compounds of germanium during the last years, opening a direct insight into the fascinating borderland 

between molecules and the solid state. [1-5] Thereby we could show that novel structural motives are 

realized in this area, e.g. the fullerene-like compound Ge14[Ge(SiMe3)3]5Li3(THF)6 1, where the 14 

germanium atoms are arranged in a hollow form. [6] 

Beside novel structural motives also novel bonding is 

present within these compounds, e.g. a multiradicaloid 

bonding character is present within 1. [7] 

Here we will describe a novel metalloid cluster 

compound of germanium Ge12{FeCp(CO)2}8[FeCpCO]2 

2, where transition metal ligands are present and where 

the polyhedron build up of the 12 germanium atoms in 

the cluster core represents a novel structural motive in 

germanium chemistry, indicating a structural transition 

onto the cubic primitive structure of α polonium. 

Ge14[Ge(SiMe3)3]5Li3(THF)6 1 

(without hydrogen atoms) 

[1] A. Schnepf, Angew. Chem. Int. Ed. 2004 43, 664 – 666. [2] A. Schnepf, Coord. Chem. Rev. 2006, 250, 

2758 – 2770. [3] A. Schnepf, Chem. Soc. Rev. 2007, 36, 745 – 758. [4] A. Schnepf, Eur. J. Inorg. Chem. 

2008, 1007 – 1018. [5] A. Schnepf, New J. Chem. 2010, 34, 2079 – 2092. [6] C. Schenk, A. Schnepf, 

Chem. Commun. 2008, 4643 – 4645. [7] C. Schenk, A. Kracke, K. Fink, A. Kubas, W. Klopper, M. 

Neumaier, H. Schnöckel, A. Schnepf, J. Am. Chem. Soc. 2011, 133, 2518 – 2524.

Plenary 5 Wednesday 8:50 a.m. 

Boron Containing Heteroacenes 

61 


Thomas K. Wood, Lauren G. Mercier, Juan F. Araneda, Benedikt Neue, Warren E. Piers and Masood 

Parvez 

(wpiers@ucalgary.ca) 

Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4 

Canada 

One way to modify the properties of extended aromatic hydrocarbons is to transpose one or more carbon 

atoms with other elements in the framework of the organic molecule. We have thus been investigating 

the chemistry of extended aromatic and antiaromatic systems that utilize boron atoms in place of CH units 

and observe the changes in properties of the resulting boracycles. Further, exchange of C-C units for 

isoelectronic B-N units is another approach we have been exploring. In order to do this, new synthetic 

methods are required; in providing an overview of our recent results in this area, this lecture will 

emphasize synthetic methodology as well as the unique properties of the boron containing analogs of the 

all carbon frameworks. Materials using antiaromatic 5 membered boroles and aromatic 6 membered 

borabenzene or 7 membered borepin rings as building blocks in heteroacenes will be discussed.

Keynote 7 Wednesday 9:30 a.m. 

C-H····X Hydrogen Bonding in Carbocation Salts 

62 


Christopher A Reed, Evgenii S. Stoyanov, Irina V. Stoyanova and Fook S. Tham 

(chris.reed@ucr.edu) 

Center for s and p Block Chemistry, University of California, Riverside, California 92521, USA 

The textbook explanation for the stability of t-butyl cation is positive charge delocalization via 

hyperconjugation. Aligned C-H bonds donate electron density into the formally empty pz orbital. There is 

no doubt that this is correct for the isolated (gas phase) cation because the gas phase IR spectrum of t-Bu + 

shows truly outstanding agreement with that calculated for the Cs symmetry structure. [1] 

Hyperconjugation was invoked by Olah in 1964 to explain the unusually low IR frequency of the C-H 

stretch (νmax 2830 cm -1 ) of t-Bu + in an SbF5 superacid matrix. [2] Near coincidence with νmax in the gas 

phase (2834 cm -1 ) has left the impression that the same explanation solely rationalizes the stability of t- 

Bu + in condensed phases. We now show that this convergence of gas and condensed phase spectral data 

was entirely fortuitous. The C-H stretch in the IR spectrum of t-Bu + in the solid state varies linearly as a 

function of anion basicity on the νNH scale 3 and requires explanation not only in terms of 

hyperconjugation but also of H-bonding (Figure). H-bonding also stabilizes benzenium ion (C6H7 + ) salts. 

[1] G. E. Douberly, A. M. Ricks, B. W. Ticknor, P. v. R. Schleyer, M. A. Duncan, J. Am. Chem. Soc., 

2007, 129, 13782. 

[2] G. A. Olah, E. B. Baker, J. C. Evans, W. S. Tolgyesi, J. S. McIntyre, Bastien, I. J. J. Am .Chem. Soc. 

1964, 86, 1360. 

[3] E. S. Stoyanov, K.-C. Kim, C. A. Reed, J. Am. Chem. Soc. 2006, 128, 8500.


Cationic Polyphosphorus Ring- and Cage-Compounds from P4 

63 


Jan J. Weigand, 1 Michael H. Holthausen, 1 Kai-Oliver Feldmann, 1 Gernot Frenking, 2 Maximilian Donath 1 

and Stephen Schulz 1 

(jweigand@uni-muenster.de) 

1 Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, 

Corrensstraße 30, 48149 Münster, Germany 

2 Institut für Anorganische Chemie, Philipps Universität Marburg, Germany 

White phosphorus is the most notable allotrope of elemental phosphorus in terms of reactivity and 

represents the entry point for the synthesis of organophosphorus compounds (OPCs). Substantial efforts 

have been devoted to the development of direct P4 functionalization to escape the traditional stages via the 

intermediacy of PCl3 and subsequent transformation reactions. In this respect we are developing general 

protocols for the formation of cationic phosphorus cages by consecutive insertion of phoshenium 

cations [1] into P-P bonds of P4 to form monocationic cages of the type [R2P5] + , [RP5Cl] + and [P5Cl2] + (R = 

alky, aryl, NR2) as well as dicationic [R4P6] 2+ and tricationic [R6P7] 3+ species. [2-5] Recently, we have been 

able to stepwise breakdown our cationic [RP5Cl] + (R = Dipp) cages by the nucleophilic reaction with 

NHCs (N-heterocyclic carbenes, L) into cationic [L2P4] 2+ , [L2P3] + , and [DippP2] + fragments which 

represent novel [P] building blocks. [6] 

[1] Weigand, J. J.; Burford, N.; Decken, A.; Schulz, A. Eur. J. Inorg. Chem., 2007, 4868. 

[2] Weigand, J. J.; Holthausen, M. H.; Fröhlich, R. Angew. Chem. Int. Ed. 2009, 48, 295. 

[3] Weigand, J. J.; Holthausen, M. H. J. Am. Chem. Soc. 2009, 131, 14210. 

[4] Holthausen, M. H.; Weigand, J. J. Z. Anorg. Allg. Chem. 2012, DOI: 10.1002/zaac.201200123. 

[5] Holthausen, M. H.; Feldmann, K.-O.; Schulz, S.; Hepp, A.; Weigand, J. J. Inorg. Chem. 2012, 131, 

3374. 

[6] Holthausen, M. H.; Richter, R.; Hepp, A.; Weigand, J. J Chem. Commun. 2010, 46, 6921.


64 


Exploitation of Boryl Substituents for the Stabilization of Novel Sub-valent 

Main Group Systems 

Andrey Protchenko, a Liban Saleh, a Krishna Hassomal Birjkumar, b Nikolas Kaltsoyannis, b Cameron 

Jones, c Philip Mountford a and Simon Aldridge a 

(Simon.Aldridge@chem.ox.ac.uk) 

a Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, 

Oxford, OX1 3QR, UK 

b Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon 

Street, London, WC1H 0AJ, UK 

c School of Chemistry, Monash University, Melbourne, VIC, 3800, Australia 

The extremely strong σ-donor capabilities of the boryl ligand, BX2 - , have been well documented in 

transition metal chemistry, as a result of extensive studies of structure and reactivity made over the last 20 

years. The use of highly sterically demanding variants as spectator ligands in the stabilization of low 

coordinate species, however, has been facilitated only recently through the synthesis of nucleophilic boryl 

reagents. [1] As a result of the availability of boryllithium species such as {(HCNDipp)2B}Li(thf)2 (Dipp = 

2,6- i Pr2C6H3), for example, the introduction of the BX2 function by reaction with metal electrophiles has 

been opened up as a new synthetic methodology. In recent work we have exploited this approach, 

together with the strong σ-donor capabilities and high steric demands of the [(HCNDipp)2B] - ligand in the 

synthesis of novel Main Group systems featuring unusual coordination numbers and/or oxidation states. 

The current presentation will focus on such systems from Groups 12-14. [2] 

As an example, boryl ancillary ligands have been exploited in the synthesis of the first example of a 

simple two-coordinate acyclic silylene, SiR2, a class of compound which has hitherto been identified only 

as a transient intermediate or thermally labile species. By making use of the [(HCNDipp)2B] substituent, 

an isolable monomeric species, Si{B(NDippCH)2}{N(SiMe3)Dipp}, can be synthesized which is stable in 

the solid state up to 130 o C (see Scheme). This silylene species undergoes facile oxidative addition 

reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C-H bonds, consistent with a low 

singlet-triplet gap (103.9 kJ mol -1 ), thus demonstrating fundamental modes of reactivity more 

characteristic of Transition Metal systems. 

[1] Segawa, Y.; Yamashita, M.; Nozaki, K. Science 2006, 314, 113. 

[2] Protchenko, A.; Birjkumar, K. H.; Dange, D.; Schwarz, A. D.; Vidovic, D.; Jones, C.; Kaltsoyannis, 

N.; Mountford, P.; Aldridge, S. submitted.


Unusual Chemical Bonds in Cyclic Ditetrylenes 

65 


Gernot Frenking 

(frenking@chemie.uni-marburg.de) 

Fachbereich Chemie, Philipps-Universität, Hans-Meerwein-Strasse, D-35043 Marburg, Germany 

Very recently, the dimer of a silaisonitrile (1) which possesses two divalent silicon atoms in a fourmembered 

ring could become isolated and structurally characterized. [1] Compound 1 which is the first 

example of a base-free disilylene has two amido groups in 1,3-position bonded to the silicon atoms. 

Another four-membered compound with two divalent group14 atoms is the digermylene 2 where the 

germanium atoms are bonded to gallium. Compound 2 has also been synthesized and its geometry could 

become determined by x-ray crystallography. [2] The lecture focuses on the unusual bonding situation in 1 

and 2 and their group-14 homologues. 

1 2 

[1] R. S. Ghadwal, H. W. Roesky, K. Pröpper, B. Dittrich, S. Klein, G. Frenking, Angew. Chem. Int. Ed. 

2011, 50, 5374–5378. 

[2] A. Doddi, C. Gemel, K. Freitag, M. Winter, R. A Fischer,C. Goedecke, H. S. Rzepa, G. Frenking, 

Angew. Chem. Int. Ed., submitted for publ.

P 

O 

Na 

Plenary 6 Wednesday 11:50 a.m. 

Phosphorus-rich Inorganic Ring Systems 

66 


Evamarie Hey-Hawkins, a Santiago Gómez-Ruiz, a,b Aslihan Kircali, a Ivana Jevtovich a and Peter Lönnecke a 

(hey@uni-leipzig.de) 

a Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany, 

b Departamento de Química Inorgánica y Analítica, E.S.C.E.T. Universidad Rey Juan Carlos, Calle 

Tulipán sn, 28933, Móstoles, Spain 

The chemistry of polyphosphorus compounds has developed impressively over the last four decades. 

Thus, a great number of cyclic and catenated polyphosphanes (both as hydrides and as organic 

derivatives) have been synthesised and successfully characterised. [1] The chemistry of these compounds 

can be analogous to that of related carbon compounds. [2] On the other hand, the chemistry of cyclic and 

catenated oligophosphanide anions has hardly been explored until recently, as selective and facile 

syntheses were mostly unknown. We have developed a simple synthetic route to the alkali metal salts 

M2(P4R4) (M = Na, K; R = Ph, t Bu, Mes) and cyclo-(P5 t Bu4) – anion, [3] which display unusual reactivity 

and intriguing chemistry. [4] 

Na(THF)3{cyclo-(P5 t Bu4)} {cyclo-(P5 t Bu4)}2 Manganese(I) complex 

Au4P20 framework of 

[Au4{P t Bu(P4 t Bu3)}4] 

Thus, MCl2 (M = Sn, Pb) and BiCl3 react with cyclo-(P5 t Bu4) – to form the novel dimers {cyclo-(P5 t Bu4)}2 

and {cyclo-(P4 t Bu3)P t Bu2}2, as well as the secondary phosphine cyclo-(P5 t Bu4H). Furthermore, a wide 

range of transition metal complexes (e.g., Zr, Ta, Cr, Mo, W, Mn, Fe, Rh, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd) 

with linear and cyclic oligophosphanide ligands is known. Besides the academic challenge, metal 

complexes with anionic polyphosphorus ligands are of interest as potential precursors for the 

development of rational syntheses of binary metal phosphides (MxPy), which are a fascinating class of 

compounds with unusual structures and interesting properties for materials science. [5] Financial support 

from the Deutsche Forschungsgemeinschaft (He 1376/22-3 and within the Graduate School of Excellence 

BuildMoNa) and the EU-COST Action CM0802 PhoSciNet is gratefully acknowledged. 

[1] See for example: M. Baudler, K. Glinka, Chem. Rev. 1993, 93,1623-1667. 

[2] K.B. Dillon, F. Mathey, J.F. Nixon, Phosphorus the Carbon Copy: From Organophosphorus to 

Phospha-organic Chemistry. Wiley, Chichester, 1998. 

[3] A. Schisler, U. Huniar, P. Lönnecke, R. Ahlrichs, E. Hey-Hawkins, Angew. Chem. Int. Ed. 2001, 40, 

4217-4219. 

[4] S. Gómez-Ruiz, E. Hey-Hawkins, in: Phosphorus Chemistry: Catalysis and Material Science 

Applications, ed. M. Peruzzini, L. Gonsalvi, Springer, Volume 37, 2011, 85-120; S. Gómez-Ruiz, E. 

Hey-Hawkins, New J. Chem. 2010, 34, 1525-1532; S. Gómez-Ruiz, E. Hey-Hawkins, in: Recent 

Trends in Main Group Chemistry, ed. T. Chivers, Coord. Chem. Rev. 2011, 255, 1360-1386; A. 

Kircali, R. Frank, S. Gómez-Ruiz, B. Kirchner, E. Hey-Hawkins, ChemPlusChem 2012 (in press, 

DOI: 10.1002/cplu.201200013). 

[5] H.-G. von Schnering, W. Hönle, Chem. Rev. 1988, 88, 243-273.

Oral 38 Thursday 8:50 a.m. 

67 


Development of a Single-Component Liquid-Phase Hydrogen Storage 

Material 

Wei Luo, Patrick G. Campbell and Shih-Yuan Liu 

(lsy@uoregon.edu) 

Department of Chemistry, University of Oregon, Eugene, Oregon 97403, USA 

The development of sustainable energy platforms is an important task because of national security, 

environmental, and financial concerns related to energy supply. New materials for hydrogen storage 

continue to be attractive toward establishing a carbon-neutral energy infrastructure. The field of chemical 

hydrogen storage has been dominated by ammonia borane (NH3–BH3, AB) and its derivatives. A 

potential new hydrogen storage platform based on well-defined carbon(C)-boron(B)-nitrogen(N) 

heterocyle materials is described. Specifically, I will discuss the development of a liquid-phase hydrogen 

storage material that is a liquid under ambient conditions, releases H2 controllably and cleanly at 80 °C, 

and does not undergo a phase change upon H2 desorption. Preliminary investigations into the mechanism 

of H2 desorption will also be discussed. 

[1] Luo, W.; Campbell, P. G.; Zakharov, L. N.; Liu, S.-Y. "A Single-Component Liquid-Phase Hydrogen 

Storage Material" J. Am. Chem. Soc. 2011, 133, 19326-19329. 

[2] Luo, W.; Zakharov, L. N.; Liu, S.-Y. "1,2-BN Cyclohexane: Synthesis, Structure, Dynamics, and 

Reactivity" J. Am. Chem. Soc. 2011, 133, 13006-13009. 

[3] Campbell, P. G.; Zakharov, L. N.; Grant, D.; Dixon, D. A.; Liu, S.-Y. "Hydrogen Storage by 

Boron-Nitrogen Heterocycles: A Simple Route for Spent Fuel Regeneration" J. Am. Chem. Soc. 

2010, 132, 3289-3291. 

[4] Staubitz, A.; Robertson, A. P.; Manners, I. “Ammonia-borane and related compounds as 

dihydrogen sources” Chem. Rev. 2010, 110, 4079-4124.

68 


Phosphazenes as Scaffolds for the Synthesis of New Molecules by Palladium 

and Copper Catalyzed Reactions 

Cemile Kumas and Patty Wisian-Neilson 

(pwisian@smu.edu) 

Department of Chemistry, Southern Methodist University, Dallas, TX 75275-0414 USA 

Both cyclic and polymeric phosphazenes with simple alkyl and aryl substituents attached by direct P-C 

bonds have been prepared by condensation reactions of N-silylphosphoranimines, Me3SiN=P(X)RR'. 

Although post-modification of methyl groups in the simple preformed phosphazenes has facilitated the 

incorporation of a variety of functional groups, variation of the aromatic groups has been more 

challenging. Several new phosphazenes with more elaborate aryl groups have now been prepared by 

condensation reactions. In addition, post-modification of the cyclic and polymeric bromophenyl 

phosphazenes, [NP(C6H4Br)CH3]n, by palladium-catalyzed cross coupling reactions have afforded a 

series of phosphazenes with wide variety of functional groups attached to the aryl ring by C-C bonds 

(Suzuki, Sonogashira, and Mizoroki-Heck reactions) and C-N bonds (Buchwald-Hartwig reactions). 

Synthetic routes to prepare cyclo- and polyphosphazenes with alkyne units attached directly to the P 

atom, [NP(C≡CR)(C6H6)]n (R = H, SiMe3, C6H5) have also been developed. Post-modification via coppercatalyzed 

alkyne-azide cycloaddition reactions was used to attach benzyl, anthracene and 

methoxyethoxyethylene groups. Preliminary studies indicated that thiol-yne and Cadiot-Chodkiewicz 

alkyne cross-metathesis reactions also have potential utility. 

Br 

N P 

CH 3 

3,n 

Pd catalyst 


R 

N P 

CH 3 

3,n 

N 

P 

C 

C 

R 

3,n 

+ 

N 3 

R' 

Cu catalyst 

R' 

N 

P 

3,n 

N 

N N


69 


Heavier Group 14 Homologues of Carbenes in The Synthesis of Heavier 

Aromatic and E(0) Compounds 

Johanna Flock, Michaela Flock, Amra Suljanovic, Petra Wilfling and Roland C. Fischer 

(roland.fischer@tugraz.at) 

Institute of Inorganic Chemistry, Graz University of Technology 

Stremayrgasse 9 V, A-8010 Graz, Austria 

The reactions of heavier group 14 homologues of carbenes with various substrates continue to be a key 

topic in main group chemistry. [1] In this context, we set out to investigate the reaction between sterically 

encumbered heavier group 14 tetrylenes Ar*2E, (E=Ge, Sn, Pb; Ar*=C6H3-2,6-Mes2) with 

phosphaalkynes, R-C≡P. In contrast to E=Sn and Pb, where bis-phosphaalkene substituted stannylenes 

and plumbylenes where isolated in good to moderate yields, the germylenes provided clean access to the 

respective germadiphospholes. [2] 

Reaction of amino pyridine ligand 1 with E[N(SiMe3)2]2 (E=Ge, Sn, Pb) provided clean access to the 

heteroleptic tetrylenes 2 and 3 for E=Sn, Pb. In the case of germanium, however, we obtained compound 

4 in good yields. [3] 

Ultimately, this chemistry enabled us to isolate compounds 5 [4] and 6, which are unprecedented examples 

of mononuclear main group element compounds in which the heavier main group atoms adopts a formal 

oxidation state of zero. 

[1] P. P. Power, Nature, 2010, 463, 171. 

[2] P. Wilfling, R. C. Fischer manuscript in preparation 

[3] J.Flock, M. Flock, R. C. Fischer, manuscript in preparation 

[4] J.Flock, A.Suljanovic, A. Torvisco, W. Schoefberger, M. Flock, R. C. Fischer, submitted


(-O-Te-N-)4 Macrocycles 

70 


Patrick Szydlowski, Phillip J.W. Elder, Joachim Kübel, Chris Gendy, Derek R. Morim, Ignacio Vargas- 

Baca 

(vargas@chemistry.mcmaster.ca) 

Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, 

Hamilton, Ontario, Canada L8S4M1 

Stringing heavy elements in a periodic sequence is key to the design and preparation of new 

macromolecular materials with unusual properties. In many cases, even when suitable precursors can be 

synthesized and reaction conditions optimized to promote the formation of long chains, the final result is 

the formation of small molecules because of the lability of the bonds made by the heaviest elements. For 

example, Te-N and Te-O combinations most commonly produce four-membered rings. An interesting 

exception was observed in the structure of 1a, [1] which formally is assembled by the spontaneous 

concatenation of tellurazole-N-oxide molecules formed in-situ. A second example (1b) of this type of 

macrocycle was recently characterized. [2] This molecule, however, features a chair conformation in 

contrast to the twisted boat of 1a. Spectroscopic studies, supported by DFT calculations, were applied to 

study the dynamic equilibrium between such conformations. The chemistry of these species, including the 

prospects of an extension to host-guest systems, will be discussed. 

[1] J. Kübel, P. J. W. Elder, H. A. Jenkins and I. Vargas-Baca, Dalton Trans, 2010, 39, 11126. 

[2] P. Szydlowski, Senior Undergraduate Thesis, McMaster University, 2012.


Macrocyclic Phosphorus(I) Oligomers 

71 


Gregory J. Farrar, Erin L. Norton, Bobby D. Ellis and Charles L. B. Macdonald 

(cmacd@uwindsor.ca) 

Department of Chemistry & Biochemistry, University of Windsor, Windsor, Ontario, Canada 

Over the last decade, we have been investigating the chemistry of compounds containing p-block 

elements in unusually low oxidation states. [1-2] For group 15, we previously developed convenient 

syntheses for compounds containing donor-stabilized P(I) ions. [3-5] Most of these compounds are air- and 

moisture-stable and some are valuable reagents for the synthesis of other stable low-oxidation state 

species using ligand replacement reactions. Importantly, the amphoteric nature of the P(I) ions makes 

them ideal main group linkers for the formation of coordination polymers using judiciously-designed 

ligands (both neutral and anionic). Some of our recent efforts regarding the synthesis and characterization 

of oligomers/macrocrocycles containing such univalent phosphorus centers, which include the 

phosphorus-rich analogues of phosphazenes, will be presented. 

[1] C. L. B. Macdonald, B. D. Ellis, in Encyclopedia of Inorganic Chemsitry, 2nd ed. (Ed.: R. B. 

King), John Wiley & Sons Ltd., 2005. 

[2] B. D. Ellis, C. L. B. Macdonald, Coord. Chem. Rev. 2007, 251, 936-973. 

[3] B. D. Ellis, M. Carlesimo, C. L. B. Macdonald, Chem. Commun. 2003, 1946-1947. 

[4] B. D. Ellis, C. L. B. Macdonald, Inorg. Chem. 2006, 45, 6864-6874. 

[5] E. L. Norton, K. L. S. Szekely, J. W. Dube, P. G. Bomben, C. L. B. Macdonald, Inorg. Chem. 

2008, 47, 1196-1203.


Novel Stannacyclopentanes – Effective Catalysts or Dead End? 

J. Binder, R. Fischer, J. Pichler, B. Seibt, A. Torvisco and F. Uhlig 

(frank.uhlig@tugraz.at) 

Institute of Inorganic Chemistry, Graz University of Technology, 

Stremayrgasse 9, A-8010 Graz, Austria 

72 


Recently dibutyltindilaureate one of the most popular catalysts for a wide variety of chemical reactions 

and applications was banned for public use in many countries worldwide. Although this was announced 

since a couple of year’s attempts to develop a real alternative were only partially successful so fare. 

Therefore, one of the main research interest of our group is focused currently on the development of novel 

cyclic, catalytic active species containing the heavy group 14 elements germanium or tin. We discuss 

here on the synthesis and analytical characterization of a series of 5-membered tin-containing ring 

systems (A - B) displaying in some cases a surprising reaction behavior. Furthermore a brief introduction 

about the catalytic activity of such derivatives will be given as well. 

Sn Sn 

z z 

Sn NH 

Scheme 1: stannacyclopentanes of type A – C (Z = Me2Si, O)


73 


Germanium(II),Tin(II) and Lead(II) Amides Containing an Adjacent 

Coordination Group 

Hana Vankatova, Jan Turek, Martin Novotny, Zdenka Padelkova and Ales Ruzicka 

(ales.ruzicka@upce.cz) 

Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of 

Pardubice, Studentska 573, Pardubice 532 10, Czech Republic 

Tetrylenes, low-valent group 14 compounds including carbenes, silylenes, germylenes, stannylenes and 

plumbylenes, are subject of growing research interest. [1] In particular, metal amides are among the most 

studied and used compounds in catalysis and new materials preparation. [2] The heavier elements of group 

14 metal amides with the metal atom in a lower oxidation state are widely accepted as carbene [3] 

(M(NR2)), radical [4] (M(NR2)3) or alkyne [5] analogs. 

Our current interest is focused on the structure and reactivity of different group 14 metal complexes 

containing [2-(dimethylamino)methyl]aniline which is able to stabilize target compounds as a bidentate 

ligand by the formation of six-membered diazametallacycle. [6] New results on this field including the 

formation of higher aggregates (dimers, trimers and tetramers) or clusters will be discussed together with 

relevant findings in groups of closely related C,N- and O,N-chelated compounds. 

Fig. 1: Schematical example of reactivity studied 

The authors would like to thank the Grant Agency of the Czech Republic (grant no. P207/12/0223) for the 

financial support. 

[1] For one of recent reviews see: Asay, M.; Jones, C.; Driess, M. Chem. Rev. 2011, 111, 254-296. 

[2] Lappert, M. F.; Protchenko, A. V.; Power, P. P.; Seeber, A. Metal Amide Chemistry; Chapter 9, 

Wiley, John Wiley and Sons, Ltd: Chichester, UK, 2009. 

[3] (a) Harris, D. H.; Lappert, M. F. J. Chem. Soc., Chem. Commun. 1974, 895-896. (b) Davidson, P. J.; 

Harris, D. H.; Lappert, M. F. J. Chem. Soc., Dalton Trans. 1976, 2268-2274. 

[4] Davidson, P. J.; Hudson, A.; Lappert M. F.; Lednor, P. W. J. Chem. Soc., Chem. Commun. 1973, 21, 

829-830. 

[5] Power, P. P. Nature 2010, 463, 171-177. 

[6] Vankatova, H; Broeckaert, L; De Proft, F; Olejnik, R; Turek, J; Padelkova, Z; Ruzicka, A, Inorg. 

Chem. 2011, 50, 9454-9464.

74 


Metallo-Organic Clathrates from Self-Assembly of a Five-Fold Symmetric 

Ligand 

Robert J. Less, [a] Thomas C. Wilson, [a] Bihan Guan, [a] Mary McPartlin, [a] Alexander Steiner, [b] Paul T. 

Wood and Dominic S. Wright [a] 

(rjl1003@cam.ac.uk, dsw1000@cam.ac.uk) 

[a] Chemistry Department, Cambridge University, Lensfield Rd., Cambridge CB2 1EW, UK 

[b] Chemistry Department, University of Liverpool, Crown Street, Liverpool L69 3BX, UK 

The pentacyanocyclopentadienide anion, Cp(CN)5 - can act as a five-fold symmetric node when 

coordinated to metal cations. This forces curvature and directs the formation polyhedral cages. 

1 


Figure 1. Pentacyanocyclopentadienide anion (1) Figure 2. Cubic-Na[1] showing channels 

(orange) and voids (yellow). 

A series of group 1 metal (Na, K, Rb, Cs) complexes with the pentacyanocyclopentadienide anion (1, 

Figure 1) have been prepared and structurally characterised. Their solid-state structures are highly 

dependent on the solvent systems used for crystallisation. 

Crystallisation of Na[1] from nitromethane / diethyl ether results in the formation of 

Na46{1}48]Na2·(MeNO2)x(Et2O)y (cubic-Na[1], Figure 2), a highly porous metallo-organic framework 

(MOF) comprising of tetrahedrally close-packed (TCP) arrangements of pentagonal-based dodecahedra 

(D) and 14-hedra (T) strongly reminiscent of type I gas hydrates 46H2O·6X·2Y (X, Y = CO2, CH4). [1] 

If, however, Na[1] is crystallised from propan-2-ol / pentane, the resulting MOF formed 

[Na{1}]45·(H2O)9·( i PrOH)x(C5H12)y is of hexagonal symmetry (hexagonal-Na[1]) and includes 15-hedra 

(P) in addition to D and T polyhedra. Heavier group 1 metal salts form highly condensed phases with no 

solvent present when crystallised under the same conditions. 

Na[1] also provides a valuable starting material with which to access a number of other metal derivatives. 

Metathesis with metal chlorides allowed the preparation of Co, Cu, Ag and Au complexes of 1. [2] 

Notably, in these complexes 1 behaves as a σ-CN donor rather than a π-donor, reflecting the electronwithdrawing 

effect of the C≡N groups on the C5-ring. 

[1] J. Bacsa, R. J. Less, H. E. Skelton, Z. Soracevic, A. Steiner, T. C. Wilson, P. T. Wood, D. S. Wright, 

Angew. Chem. Int. Ed. 2011, 50, 8279-8282. 

[2] R. J. Less, T. C. Wilson, M. McPartlin, P. T. Wood, D. S. Wright, Chem. Commun. 2011, 47, 10007- 

10009; R. J. Less, B. Guan, N. M. Mureson, M. McPartlin, E. Reisner, T. C. Wilson, D. S. Wright, 

Dalton Trans. 2012, 41, 5919-5924.

75 


Inorganic Rings and Chains via Condensation Reactions of Silylamino, 

Silylimino, and Silylanilino Derivatives of Phosphorus and Boron 

Robert H. Neilson 

(R.Neilson@tcu.edu) 

Department of Chemistry, Texas Christian University, Fort Worth, TX 76129, USA 

The chemistry of phosphorus and boron compounds that contain silicon-nitrogen functional groups is 

both diverse and synthetically useful. The variety of reactions that occur at phosphorus or boron, in 

combination with facile cleavage of the Si-N bond, makes them potential precursors to many types of 

acyclic, cyclic, and polymeric P-N and B-N systems. For example, most condensation polymerization 

routes to phosphazene polymers are based on the high reactivity of Si-N=P compounds known as Nsilylphosphoranimines. 

In a similar vein, we have also been investigating related systems in which the 

Si-N moiety is attached to a 4-substituted phenyl group as in the title silylanilino derivatives. Some of 

these systems are being studied as precursors to new types of inorganic ring systems and/or inorganicorganic 

hybrid polymers. Within this broad context, representative examples of the synthesis and 

reactivity of precursors of types 1 - 3 will be discussed. 

R 

Me 3 Si N P 

R' 

N P OR f 

R' R" 


1: R, R', R" = Me, Ph, ORf , CH2SiMe3 Rf = CH2CF3 R 

Me3Si N P X 

R' 

Me3Si R 

N E 

R' 

X 

3: X = Br, OCH 2 CF 3 

R, R' = Me, Ph, OCH 2 CF 3 

2: E = P, B 

X = Br, SiMe 3


76 


Synthesis and Reactivity of the BN Analog of Ethylcyclobutane, (Bcyclodiborazanyl)amine-borane: 

Implications for Selective Catalyzed 

Dehydrogenation of Ammonia-borane 

Hassan Kalviri, Felix Gaertner and R. Tom Baker 

(rbaker@uottawa.ca) 

Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, 

Ottawa, ON K1N 6N5 Canada 

Ammonia-borane (H3N•BH3, AB) has been identified as a promising material for chemical hydrogen 

storage. [1] Previous work has demonstrated that metal complexes serving as catalysts to release > 2 equiv. 

of H2 from AB selectively produce the unusual aminoborane trimer, (B-cyclodiborazanyl)amine-borane, 

1, the BN analogue of ethylcyclobutane. [2] Both computational [2] and experimental work [3] indicate that 1 

arises from the unconventional oligomerization of reactive aminoborane, H2B=NH2, through the 

intermediacy of the unsymmetrical linear ‘dimer’, H3BNH2BHNH2 that results from the well-known 

basicity of H on B. After some years of effort, a new synthetic route using the Schwartz reagent, 

Cp2ZrHCl, and AB affords a 40% yield of 1 and allows for detailed studies of its reactivity and a 

comparison with its well-known BN cyclohexane isomer, cyclotriborazane, 2. 

[1] Stephens, F. H.; Pons, V.; Baker, R. T. Dalton Trans. 2007, 2613; Marder, T. B. Angew. Chem. Int. 

Ed. 2007, 46, 8116; Hamilton, C. H.; Baker, R. T.; Staubitz, A.; Manners, I. Chem. Soc. Rev. 2009, 

38, 279; Staubitz, A.; Robertson, A. P. M.; Manners, I. Chem. Rev. 2010, 110, 4079. 

[2] Pons, V.; Baker, R. T.; Szymczak, N. K.; Heldebrant, D. J.; Linehan, J. C.; Matus, M. H.; Grant, D. J.; 

Dixon, D. A. Chem. Commun. 2008, 6597. 

[3] Shaw, W. J.; Linehan, J. C.; Szymczak, N. K.; Heldebrant, D. J.; Yonker, C.; Camaioni, D. M.; Baker, 

R. T.; Autrey, T. Angew. Chem. Int. Ed. 2008, 47, 7493.


77 


Exploring the Isoelectronic and Isolobal Analogies in Inorganic Ring Systems 

– Studies in Free Radical Chemistry 

John J. Hayward and Jeremy M. Rawson 

(jhayward@uwindsor.ca, jmrawson@uwindsor.ca) 

Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON, N9B 

3P4, Canada 

A variety of 7π-electron inorganic free radicals are known and their physical properties are well 

documented. [1] The design of new ring systems involves the application of concepts of isomerism, 

isolobalism and isoelectronicity; the use of alternative p-block elements therefore provides many different 

options for the construction of new ring systems. The different aspects of the bonding in such systems 

which have recently been studied by the Rawson group will be presented, particularly with respect to 

radical stabilisation. 

[1] J. M. Rawson , A. Alberola and A. Whalley, J. Mater. Chem., 2006, 16, 2560 – 2575.


Molecular Heterobimetallic Gallo- and Alumoxanes 

78 


Monica Moya-Cabrera § , Ricardo Peyrot, Erandi Bernabé-Pablo and Vojtech Jancik § 

(monica.moya@unam.mx) 

Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carr. Toluca-Atlacomulco, 

C.P. 50200, Toluca, Estado de México, México. § Academic staff from the Universidad Nacional 

Autónoma de México 

Alumoxanes are important catalysts and co-catalysts in the polymerization of a broad variety of organic 

molecules and their chemistry has been thoroughly under investigation in the last decades. [1] Nonetheless, 

structurally modified alumoxanes remain a synthetic challenge, mainly due to their difficulty to crystallize 

in low aggregation and crystalline forms. Indeed, tailor-made alumoxanes, particularly those bearing soft 

atoms are unknown to date. Albeit, the presence of both hard and soft donor atoms bound to Al can lead 

to a change in the properties of the metal center and thus, to an overall modification of their chemical 

behavior. In this regard, we have reported on the preparation of the molecular alumoxane hydroxide and 

hydrogen sulfide [{LAl(EH)}2(µ-O)] ((L = HC[(CMe)N(2,4,6-Me3C6H2)]2 – ); E = O(1), S(2)) under very 

mild conditions. [2] 

Herein, we report on the preparation of the unique group 4 and lanthanide heterobimetallic ring systems 

derived from 1 and 2, as well as on the molecular galloxane [{LGa(OH)}2(µ-O)] (3) and its group 4 

heterobimetallic complexes (Figure 1). These heterobimetallic systems may be used as model compounds 

for structural analyses, elucidation of catalytic mechanisms, as well as precursors in the synthesis of 

heterogeneous systems. Furthermore, the presence of two different metals arranged in close proximity can 

lead to a cooperative or simultaneous activation of substrate molecules. [3] 

Figure 1. Molecular alumoxanes and galloxanes containing Nd and Zr, respectively. 

[1] (a) Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99. (b) Feng, T. L.; Gurian, P. L.; 

Healy, M. D.; Barron, A. R. Inorg. Chem. 1990, 29, 408. c) Y. Koide, S. G. Bott, A. R. Barron, 

Organometallics 1996, 15, 2213. (d) Galimberti, M.; Destro, M.; Fusco, O.; Piemontesi, F.; Camurai, 

I. Macromolecules 1999, 32, 258. (e) Kaminsky, W. Catal. Today 2000, 62, 23. (f) Watanabi, M.; 

McMahon, C. N.; Harlan, C. J.; Barron, A. R. Organometallics 2001, 20, 460. 

[2] González-Gallardo, S. Jancik, V. Cea-Olivares, R. Toscano, R. A. Moya-Cabrera M., Angew. Chem. 

Int. Ed. 2007, 46, 2895 – 2898. 

[3] Mandal, S. K.; Roesky, H. Acc. Chem. Res. 2010, 43, 248, and references cited therein.


79 


Electrochemical and Spectroelectrochemical Sharacterization of Redox-active 

Main Group Compounds: Monomers, Dimers, Rings and Cages 

R. T. Boeré 

(boere@uleth.ca) 

Department of Chemistry & Biochemistry, University of Lethbridge, Lethbridge, AB, Canada 

The application of modern electrochemical methods to air- and moisture-sensitive main group compounds 

provides powerful ways to characterize redox changes and electron transfer reactions. I will discuss the 

practice and promise of such techniques, including voltammetry (CV, square wave, rotated-disk), 

electrolysis, UV-visible spectroelectrochemistry and simultaneous electrochemistry electron paramagnetic 

resonance (SEEPR) spectroscopy. The application of such methods to a variety of main group compounds 

will feature, by way of illustration, monomers, dimers, rings and cage compounds of elements drawn 

largely from Groups 15 and 16. 

[1] R. T. Boeré, T. L. Roemmele and X. Yu, Inorg. Chem., 2011, 50, 5123-5136. 

[2] , T. Chivers, T. L. Roemmele and H. M. Tuononen, Inorg. Chem., 2009, 48, 7294-7306. 

[3] . Chivers, Inorg. Chem., 2009, 48, 9454-9462. 

[4] R. T. Boeré, A. M. Bond, T. Chivers, S. W. Feldberg and T. L. Roemmele, Inorg. Chem., 2007, 46, 

5596-5607. 

[5] R. T. Boeré, A. M. Bond, S. Cronin, N. W. Duffy, P. Hazendonk, J. D. Masuda, K. Pollard, T. L. 

Roemmele, P. Tran and Y. Zhang, New. J. Chem., 2008, 32, 214.


Nanometric Molecular Heterometallic Silicates 

80 


Vojtech Jancik, * Miguel A. Velázquez-Carmona, Libia González-Mirelles, Eduardo Herappe-Mejía, Raúl 

Huerta-Lavorie, Diego Solis-Ibarra, Marisol Reyes-Lezama, Nieves Zavala-Segovia 

(vjancik@unam.mx) 

Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carr. Toluca Atlacomulco km. 

14.5, C.P. 50200, Toluca, Estado de México, México. *Academic staff from the Universidad Nacional 


An important component of the earth’s crust are multimetallic silicates and alumosilicates, which is 

reflected in its elemental composition (46.6% O, 27.8% Si, 8.1% Al). Many of these minerals belong to 

the family of zeolites and contain different tridimensional connectivity and arrangements, which often 

result in the formation of infinite channels in the structure. The preparation of materials of this nature, 

which contain silicon and one or more different metals directly incorporated in the inorganic framework 

is still a challenge, mainly due to the lack of control over their distribution. Thus, it is desirable to have a 

single source precursors with all necessary metal atoms already connected to silicate moieties. Herein, 

we report on molecular heterobimetallic alumo- and gallosilicates with group 4 or lanthanide metals with 

inorganic cores of 0.8 – 1.3 nm. Figure 1 presents one example of such alumotitanosilicate with 3R and 

4R rings connected in a spiro fashion, based on molecular precursors reported recently by our group. [1] 

Figure 1. Molecular structure of an aluminotitanosilicate with thermal ellipsoids at 50 % probability only 

for noncarbon atoms. Hydrogen atoms have been omitted for clarity. 

[1] a) F. Rascón-Cruz, R. Huerta-Lavorie, V. Jancik, R. A. Toscano, R. Cea-Olivares, Dalton Trans. 

2009, 1195–1200. b) V. Jancik, F. Rascón-Cruz, R. A. Toscano, R. Cea-Olivares, Chem. Commun. 

2007, 4528–4530. c) R. Huerta-Lavorie, F. Rascón-Cruz, D. Solis-Ibarra, N. Zavala-Segovia, V. 

Jancik, Eur. J. Inorg. Chem. 2011, 4795–4799. d) D. Solis-Ibarra, M. de J. Velasquez-Hernandez, R. 

Huerta-Lavorie, V. Jancik, Inorg. Chem. 2011, 50, 8907–8917. e) M. A. Velásquez-Carmona, Libia 

González-Mireles, Vojtech Jancik, manuscript en preparation. f) R. Huerta-Lavorie, D, V. Báez- 

Rodríguez, V. Jancik, manuscript en preparation.


Oxidation of Heterocyclic Phosphenium Cations 

81 


Arthur D. Hendsbee, Nick A. Giffin and Jason D. Masuda 

(Jason.masuda@smu.ca) 

The Maritimes Centre for Green Chemistry and the Department of Chemistry, Saint Mary's University, 

Halifax, Nova Scotia, B3H 3C3, Canada 

In the continuing research of low valent and low oxidation state carbon and phosphorus centers, our 

research group has recently focused on the chemistry of cationic heterocyclic phosphorus systems. 

Our developments in the reactivity of heterocyclic phosphenium cations with terminal O-N compounds 

and various heterocycles has proven to be fruitful. 

1. We have explored the reactivity of these systems with N-oxides. In particular, we have isolated a series 

of Lewis base stabilized oxophosphonium (aka phosphacylium) cations that have terminal P=O 

fragments. 

2. We also see oxygen abstraction from the stable radical TEMPO ((2,2,6,6-Tetramethylpiperidin-1yl)oxyl). 

The possible formation of a transient nitrenium cation will be discussed


82 


Stabilization by O,C,O-Coordinating Pincer-Type Ligands: From Tin(IV) to 

Sn(0)? Low-valent Organotin Compounds and their Transition Metal 

Complexes 

Klaus Jurkschat 

(klaus.jurkschat@tu-dortmund.de) 

Lehrstuhl für Anorganische Chemie II der Technischen Universität, Otto-Hahn-Str. 6, 

44227 Dortmund, Germany 

The syntheses, characterization by state-of-the-art analytical methods, and evaluation by DFT 

calculations of the bonding situations of the compounds A – K is reported. Of particular interest are the 

organotin(I) compounds of types C and D, and the unprecedented platinum complexes H – K. 

[1] a) V. Deáky, M. Schürmann, K. Jurkschat, Z. Anorg. Allg. Chem., 2009, 635, 1380; (b) M. Henn, V. 

Deáky, S. Krabbe, M. Schürmann, M. H. Prosenc, S. Herres-Pawlis, B. Mahieu, K. Jurkschat, Z. 

Anorg. Allg. Chem., 2011, 637, 211; (c) M. Wagner, K. Dorogov, M. Schürmann, K. Jurkschat, 

Dalton Trans., 2011, 40, 8839; (d) M. Wagner, C. Dietz, S. Krabbe, S. G. Koller, C. Strohmann, K. 

Jurkschat, Inorg. Chem., 2012, DOI: 10.1021/ic3005954.

83 


Revisiting a Highly Unusual Phosphine: Structure and Reactivity of P7H3 

Hongsui Sun, a Javier Borau-Garcia, a Gary D. Enright b and Roland Roesler a 

(roesler@ucalgary.ca) 

Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4 

Canada, and Steacie Institute for Molecular Sciences, 100 Sussex Drive, Ottawa, Ontario, K1A 0R6, 

Canada 

P7H3 is a highly unusual phosphine that was described by Baudler more than three decades ago. It is a 

yellow crystalline solid that resembles sulfur in appearance, it is air stable and lacks the typical 

phosphines smell, and it does not sublime or melt without decomposition. It proved insoluble in all 15 

solvents tested by the authors, including P2H4 and molten white phosphorus. [1] A solution 31 P NMR 

spectrum conducted on freshly prepared P7H3 before its precipitation from solution confirmed the 

presence of two diastereoisomers featuring the same bicyclic framework. [2] This was in good agreement 

with the synthesis of P7H3 via hydrolysis of P7(SiMe3)3, however, it did not account for its chemical and 

physical properties. 

Assuming that the unusual properties of P7H3 would be due to either strong intermolecular interactions or 

polymerization, leading to the formation of a very stable crystal lattice, we set to determine the solid state 

structure of this material using diffraction techniques, as well as mass spectrometry. The results of these 

studies, as well as the reactivity of P7H3 towards N-heterocyclic carbenes, will be presented. 

Figure 


[1] M. Baudler, H. Ternberger, W. Faber, J. Hahn, Z. Naturforsch. 1979, 34B, 1690-1697. 

[2] M. Baudler, R. Riekenhof-Böhmer, Z. Naturforsch. 1985, 40B, 1424-1429.


Synthesis of Functionalized Bicyclo[222]octasilanes 

84 


B. Hasken and H. Stüger 

(bernd.hasken@tugraz.at) 

Institute for Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9, A-8010 Graz 

There exists pronounced evidence, that electronic coupling of donor and acceptor substituent groups via 

rigid oligosilane bridges can be a rather effective process. [1] In this context the present paper describes 

novel preparative approaches to dipolar oligosilane model substances with donor and acceptor moieties 

connected by the dodecamethylbicyclo-[2.2.2]-octasilane framework (1), which has been successfully 

prepared and functionalized just recently by Marschner et al. in a pioneering study. [2] Our initial results, 

however, quickly revealed that the rigid structure of 1 apparently prevent successful nucleophilic 

substitution reactions at the brominated bridgehead silicon atoms from 3. 1, however, can be successfully 

functionalized when the polarity of the precursors is reversed. 

Scheme 1: Functionalization of a bicyclo[222]octasilane. 

A totally different approach is to synthesize already functionalized bycyclo[222]octasilane cages as 

shown in scheme 2. [3] 

Scheme 2: Synthesis of a phenylated bicyclo[222]octasilane. 

[1] H. Tsuji, J. Michl, K. Tamao, J. Organomet. Chem.685 (2003) 9 

[2] R. Fischer, T. Konopa, S. Ully, J. Baumgartner, C. Marschner, J. Organomet. Chem.685 (2003) 79 

[3] C. Krempner, U. Jäger-Fiedler, C. Mamat, A. Spannenberg, K. Weichert New J. Chem., 29 (2005) 

1581

Plenary 7 Thursday 1:40 p.m. 

85 


Accessing the Inaccessible: Molecular Magnesium(I) Compounds as Specialist 

Reducing Agents for the Synthetic Chemist 

Cameron Jones 

(cameron.jones@monash.edu) 

School of Chemistry, Monash University, Melbourne, VIC, 3800, Australia 

The chemistry of compounds containing p-block elements in very low oxidation states has rapidly 

advanced over the last two decades. More than being just chemical curiosities, these species have begun 

to find a variety of applications in synthesis, small molecule activations etc. [1] In 2007, we extended this 

field to the s-block with the preparation of the first room temperature stable molecular compounds 

containing magnesium-magnesium covalent bonds, viz. LMgMgL (L = bulky guanidinate or βdiketiminate 

1). [2] Subsequently, we have found such magnesium(I) compounds to have considerable 

utility as soluble, selective, stoichiometric reducing agents in organic and inorganic synthesis. In many 

cases, the products obtained from reactions involving these compounds are not accessible using 

traditional reducing agents, e.g. alkali metals or SmI2. This is especially so for reductions of p-block 

element precursors, which have yielded a variety of unprecedented low oxidation state group 13 and 14 

complex types, e.g. 2-5. [3] Examples of these compounds, e.g. 5, are emerging as powerful reagents for 

the facile, "transition metal-like" activation of H2, CO2, NH3 etc. In this lecture, our recent efforts to 

develop the chemistry of magnesium(I) dimers and very low oxidation state p-block compounds will be 

presented. 

[1] (a) P.P. Power, Nature, 2010, 463, 171; (b) M. Asay, C. Jones, M. Driess, Chem. Rev., 2011, 111, 

354. 

[2] S.P. Green, C. Jones, A. Stasch, Science, 2007, 305, 1136. 

[3] (a) J. Li, C. Schenk, C. Goedecke, G. Frenking, C. Jones, J. Am. Chem. Soc., 2011, 133, 18622; (b) 

W.D. Woodul, E. Carter, R. Müller, A.F. Richards, A. Stasch, M. Kaupp, D.M. Murphy, M. Driess, 

C. Jones, J. Am. Chem. Soc., 2011, 133, 10074; (c) S.J. Bonhady, D. Collis, G. Frenking, N. 

Holzmann, C. Jones, A. Stasch, Nature Chem., 2010, 2, 865.

Keynote 11 Thursday 2:20 p.m. 

Simple Ligands, Not so Simple Chemistry! 

86 


Paul J. Ragogna and Allison L. Brazeau 

(pragogna@uwo.ca) 

Department of Chemistry and the Center for Advanced Materials and Biomaterials Research 

Western University, 1151 Richmond St, London, Ontario, N6A 5B7, Canada 

Over the last several years, work in our group has centered on developing new structure and bonding 

motifs for the main group elements, specifically for elements in group 15 and 16. To push forward in this 

area, we have adapted simple ligand sets used widely within the d-block, for use in our chemistry. Two 

such examples are the pyridyl tethered 1,2-bis(imino)acenaphthene (1) (a.k.a. “clamshell”) and the 

dianionic guanidinate ligands (2). Both display rather predictable chemistry for the transition metals, but 

not so for the group 15 elements (P, As, Sb). Specific examples for each ligand set will be presented, 

where most interesting is the reluctance of the P-X bond (X = Cl, Br) within the 4-membered 

diguanidainate rings to undergo halide abstraction. 

N 

N N 

N 

R 

R N N R 

1 2 

[1] D. H. Leung, J. W. Ziller and Z. Guan, J. Am. Chem. Soc., 2008, 130, 7538–7539. 

[2] A. L. Brazeau, M. Hänninen, H. Tuononen, N. D. Jones, P. J. Ragogna J. Am. Chem. Soc. 2012, 134, 

5398-5414. 

[3] A. L. Brazeau, N. D. Jones, P. J. Ragogna Dalton. Trans. 2012 41 7890-7896. 

[4] A. L. Brazeau, A. S. Nikouline, P. J. Ragogna Chem. Commun. 2011, 47, 4817-4819. 

[5] A. L. Brazeau, C. A. Caputo, C. D. Martin, N. D. Jones and P. J. Ragogna Dalton Trans. 2010, 39, 

11069-11073.


Lewis Acidic Properties of Heavy Group 15 and 16 Compounds 

87 


Casey Wade, Tzu-Pin Lin, Iou-Sheng Ke, James Jones and François P. Gabbaï 

(francois@tamu.edu) 

Department of Chemistry, Texas A&M University, 3255 TAMU, College Station, Texas 77843-3255, USA 

As part of our ongoing investigations in the chemistry of main group Lewis acids, we have recently 

become interested in the properties of heavy pnictogenium [1] and chalcogenium ions. [2] Owing to the 

electropositive character of the central atom as well as to the presence of low lying vacant orbitals, these 

onium ions behave as unusual Lewis acids. In this presentation, we will illustrate some of these 

characteristics by describing how derivatives containing stibonium or telluronium ions can be used for the 

selective complexation of fluoride ions in protic solvents. We will also show that heavy pnictogen can 

behave as Z-ligands and engage electron rich transition metals in unusual donor acceptor interactions. [3] 

B 

F 

Sb 

Left: Fluoride anion complexation by a bidentate stibonium borane. Right: Synthesis of a gold-antimony 

derivative featuring a Au→Sb bond. 

[1] a) C. R. Wade, F. P. Gabbaï, Organometallics 2011, 30, 4479-4481; b) C. R. Wade, I.-S. Ke, F. P. 

Gabbaï, Angew. Chem. 2012, 124, 493-496; Angew. Chem. Int. Ed. 2012, 51, 478-481. 

[2] H. Zhao, F. P. Gabbaï, Nat. Chem. 2010, 2, 984-990. 

[3] a) C. R. Wade, F. P. Gabbaï, Angew. Chem., 2011, 123, 7507-7510; Angew. Chem. Int. Ed. 2011, 50, 

7369-7372; b) C. R. Wade, T.-P. Lin, R. C. Nelson, E. A. Mader, J. T. Miller, F. P. Gabbaï, J. Am. 

Chem. Soc. 2011, 133, 8948-8955; c) T.-P. Lin, C. R. Wade, L. M. Pérez, F. P. Gabbaï, Angew. 

Chem., 2010, 122, 6501-6504; Angew. Chem. Int. Ed. 2010, 49, 6357-6360; d) T.-P. Lin, R. C. 

Nelson, T. Wu, J. T. Miller, F. P. Gabbai, Chem. Sci. 2012, 3, 1128-1136; e) T.-P. Lin, I.-S. Ke, F. P. 

Gabbaï, Angew. Chem. Int. Ed. 2012, early view.


88 


Catalytic and Stoichiometric Bond-Forming Reactions Using Main Group 

Metals 

Dominic S. Wright 

(dsw1000@cam.ac.uk) 

Chemistry Department, Cambridge University, Lensfield Rd., Cambridge CB2 1EW UK 

The dehydrocoupling of element-H bonds (equ. 1) has been dominated by transition metal reagents and 

catalysts. However, it is becoming clear that high reactivity and catalytic activity can also be obtained in 

this type of reaction using main group metal-based systems (even in the absence accessible d-orbitals in 

the valence shell). Redox-active main group bases like M(NMe2)n (M = can be highly effective in the 

stoichiometric dehydrocoupling of P-P and even N-N bonds, with some unusual reactivity being 

observed. [1,2] Surprisingly, even simple Sn(IV) organometallics like Cp*2SnCl2 can function as catalysts 

in the formation of P-P bonds and are directly analogous in their behaviour to transition metal systems 

based on Zr(IV). [3] This behaviour can also be extended to other dehydrocoupling reactions. Al(III) 

amides have been shown to be as active as a number of precious metal catalysts in the dehydrocoupling of 

B-N bonds, and exhibit closely related reaction characteristics. [4,5] Where more redox-active group 13 

metals are employed unique chemistry can be observed (which is not seen for transition metals). A case in 

point is the reaction of Ga{N(SiMe3)2}3 with NH3BH3 which gives the unusual product 1 (below), in 

which a combination of B-N coupling and N(SiMe3)2 ligand rearrangement has occurred. [5,6] 

[1] R. J. Less, R. Melen, V. Naseri, D. S. Wright, Chem. Commun., 2009, 4929. 

[2] R. J. Less, .V. Naseri, M. McPartlin, D. S. Wright, Chem. Commun. 2011, 47, 6129. 

[3] V. Naseri, R. J. Less, M. McPartlin, R. E. Mulvey, D. S. Wright, J. Chem. Soc., Chem. Commun., 

2010, 46, 5000. 

[4] H. Cowley, R. L. Melen, J. M. Rawson, D. S. Wright, Chem Commun., 2011, 47, 2682. 

[5] M. M. Hansmann, R. L. Melen, D S. Wright, Chem. Sci., 2011, 2, 1554. 

[6] see also, R. J. Less, R. L. Melen, D. S. Wright, RSC Adv., 2012, review, in press. 

1

Plenary 8 Thursday 4:10 p.m. 

89 


Challenges in Metal Oxo Cluster Chemistry for Energy-Saving Materials and 

Catalysis 

Yilmaz Aksu, Kerim Samedov, Johannes Pfrommer and Matthias Driess 

(matthias.driess@tu-berlin.de) 

Technische Universität Berlin, Institute of Chemistry: Metalorganics and Inorganic Materials, Strasse 

des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany 

Current research activities in materials chemistry are devoted to the development of innovative and 

abundant materials suitable for conversion and storage of solar energy into chemicals (artificial 

photosynthesis). At the same time, there is an enormous demand for innovative new materials for energysaving 

in electronic devices. Transparent conducting oxides (TCOs) are key components in organic light 

emitting diodes (OLED’s) for solar cells, photocatalysts, transparent electrodes in displays and Field 

Effect Transistors (FET). Unfortunately, transparent electrodes in flat-panel technology, photovoltaics or 

FETs rely on expensive indium tin oxide (ITO; In2O3:Sn doped with 5% Sn) which generate a bottleneck 

for the growing demand, combined with the relatively low abundance of indium. Changing the chemistry 

and using alternative materials systems based on abundant metal oxides provides a solution: Applying the 

concept of molecular metalorganic single-source precursors opened new doorways to innovative new 

TCO materials for various applications, including bioelectrocatalysis (Fig. 1). [1-6] In my talk the synthesis 

of new main group metal-oxo cluster precursors for reliable access to inexpensive and urgently needed 

multi-metal oxides for energy-saving and photocatalysis (artificial photosynthesis) will be discussed. 

Fig. 1. From a molecular In(I)-Sn(II) oxo cage 

to a bioelectrocatalytic device.[5] 

[1] Y. Aksu, M. Driess, Angew. Chem. Int. Ed. 2009, 48, 7778. 

[2] Y. Aksu, T. Lüthge, R. Fügemann, M. Inhester, M. Driess, „Transparent electrical conducting layers: 

Procedure to prepare the layers and their applications”, Patent Appl. 2006E00310DE (Germany) and 

102007013181.1 (China, USA) 

[3] Y. Aksu, S. Jana, M. Driess, Dalton Trans. 2009, 1516. 

[4] M. Tsaroucha, Y. Aksu, E. Irran, M. Driess, Chem. Mater. 2011, 23, 2428–2438. 

[5] Y. Aksu, S. Frasca, U. Wollenberger, M. Driess, A. Thomas, Chem. Mater. 2011, 23, 1798–1804. 

[6] K. Samedov, Y. Aksu, M. Driess, Chem. Eur. J. 2012, accepted. 

Acknowledgment: We thank the Cluster of Excellence “UniCat”, financed by the DFG and administered 

by the TU Berlin, and the BMBF (L2H) for financial support.

Poster 1 

90 


Merging the Chemistry of Electron-Rich Olefins (ERO) with Imidazolium 

Ionic Liquids 

Cody N. Sherren, a Changhua Mu, b Michael I. Webb, b Iain McKenzie, b Brett M. McCollum, b Jean-Claude 

Brodovitch, b Paul W. Percival, b Tim Storr, b Kenneth R. Seddon, c Jason A. C. Clyburne a and Charles J. 

Walsby b 

(Jason.Clyburne@smu.ca) 

a Maritimes Centre for Green Chemistry, Department of Chemistry, Saint Mary’s University, Halifax, NS, 

B3H 3C3, Canada, 

b Department of Chemistry, Simon Fraser University, Burnaby, BC V5A 1S6, Canada 

c School of Chemistry and Chemical Engineering, Queen’s University, Belfast, BT7 1NN, Northern 

Ireland, UK 

Ionic liquids (ILs) have attracted attention because of their potential applications in various industrial 

settings. This report will survey some chemistry of simple molecular species with structurally simple 

reagents in ionic media. The chemistry of N-heterocyclic carbenes is intimately associated with chemistry 

observed in imidazolium based ionic liquids. Likewise, the chemistry of Electron-Rich Olefins (ERO) 

was important in the early understanding of NHCs, and EROs possess chemistry that is unique among 

alkenes. The link and relevance of EROs and IL chemistry has been ignored even though there is some 

evidence indicating its role. Here we report that the ionic liquid 1-ethyl-3-methylimidazolium 

tetrachloroaluminate(III) reacts with lithium to produce a persistent radical, which can be considered a 

hydrogen-atom adduct of an electron-rich olefin (ERO). Reaction of tetrakis(dimethylamino)ethene, a 

bona fide ERO, with muonium, produces a structurally similar radical. These results demonstrate the 

importance of ERO chemistry to applications of ionic liquids, particularly where charge carrying in basic 

conditions is important, such as in photocells.

Poster 2 

Synthesis, Reactivity and Ring-opening Polymerization (ROP) of 

[V(η 5 -C5H4)(η 7 -C7H6)Sn t Bu2] 

91 


Klaus Dück and Holger Braunschweig 

(klaus.dueck@uni-wuerzburg.de) 



During the last decades the interest in poly(metallocenes) considerably increased, because these materials 

have proven their suitability in technical applications, such as nanotechnologies or metal-based 

ceramics. [1−3] Due to the weakness of the bond between the ipso-carbon and the tin-atom, tin-bridged 

ansa-complexes are attractive for ROP reactions. [4] 

The first tin-bridged [1]trovacenophane, [V(η 5 -C5H4)(η 7 -C7H6)Sn t Bu2] (2), is synthesized by saltelimination 

reaction between [V(η 5 -C5H4Li)(η 7 -C7H6Li)]⋅pmdta (1) and Cl2Sn t Bu2. The purple crystalline 

solid is isolated in moderate yields and characterized by common spectroscopic methods, which confirm 

the strained nature of the molecule. The treatment of [V(η 5 -C5H4)(η 7 -C7H6)Sn t Bu2] with [Pt(PEt3)3] 

affords the platinastanna[2]trovacenophane 3, whereupon the Pt(0)-fragment exclusively inserts into the 

bond between the ipso-Carbon of the C7H6-ring and the bridging tin-atom. Ring-opening polymerization 

reaction of [V(η 5 -C5H4)(η 7 -C7H6)Sn t Bu2] was performed in the presence of Karstedt catalyst, yielding the 

corresponding poly(trovacenylstannan) 4. 

[1] Arsenault, A. C.; Miguez, H.; Kitaev, V.; Ozin, G.A.; Manners, I.; Adv. Mater. 2003, 15, 503. 

[2] Rehahn, M.; Bellas, V.; Angew. Chem., 2007, 119, 5174; Angew. Chem. Int. Ed. 2007, 46, 5082. 

[3] Adams, J. A.; Braunschweig, H.; Fuß, M.; Kraft, K.; Kupfer, T.; Manners, I.; Radacki, K.; Whittel, 

G. R.; Chem. Eur. J. 2011, 17, 10379. 

[4] Elschenbroich, C.; Organometallchemie 2008, 6. überarbeitete Auflage, Teubner Verlag / GWV 

Fachverlage GmbH, Wiesbaden.

Poster 3 

92 


Probing the Effect of Base-stabilization in Boryl and Borylene Complexes 

Holger Braunschweig and Thomas Kramer 

(thomas.kramer@uni-wuerzburg.de) 



Fundamental studies on transition metal complexes containing well-defined two-electron-two-centre M–B 

bonds have become an area of great interest due to the appearance of boryl complexes as key 

intermediates in a range of catalytic reactions and their remarkably strong σ-donation abilities. The extent 

of π-backdonation in these complexes was first determined by occupying the vacant p orbital of an iron 

dihaloboryl complex by a Lewis base, and the resulting changes in the M−B bond distance were 

compared to the parent compound (see following scheme). [1-3] 

The reaction of the base-stabilized dichloroboryl complex with a halide abstracting reagent provided 

access to the first cationic base-stabilized chloroborylene complex analogous to literature-reported basestabilized 

aminoborylene complexes of Aldridge. Though these compounds are formally borylene 

species, a trigonal planar coordination at the boron atom is observed, similar to boryl complexes. [4] 

Abstraction of the Lewis base leading to the first cationic chloroborylene complex is a future goal of this 

project. 

[1] G. J. Irvine, M. J. G. Lesley, T. B. Marder, N. C. Norman, C. R. Rice, E. G. Robins, W. R. Roper, G. 

R. Whittell, L. J. Wright, Chem. Rev. 1998, 98, 2685–2722. 

[2] H. Braunschweig, R. D. Dewhurst, A. Schneider Chem. Rev. 2010, 110, 3924–3957. 

[3] H. Braunschweig, K. Radacki, F. Seeler, G. R. Whittell, Organometallics 2006, 25, 4605–4610. 

[4] S. Aldridge, C. Jones, T. Gans-Eichler, A. Stasch, D. L. Kays (nee Coombs), N. D. Coombs, D. J. 

Willock, Angew. Chem. Int. Ed. 2006, 118, 6264–6268.

Poster 4 

Metalloborylene Complexes Showing a Wide Range of Reactivity 

93 


Holger Braunschweig and Katharina Ferkinghoff 

(katharina.ferkinghoff@uni-wuerzburg.de) 



The highly reactive borylene base-free ligand −BR, only stabilized in the coordination sphere of transition 

metal fragments, established the class of bridged [1] and terminal [2] borylene complexes. These compounds 

do not only show an amazing thermodynamic stability, but also a widespread pattern of reactivity. For 

instance, the terminal ferroborylene unit of [{(η 5 -C5Me5)Fe(CO)2)} (µ2-B){Cr(CO)5}] (1) can either be 

transferred to an alkyne fragment to form ferroborirenes 2-5, [3] or via intermetallic borylene transfer to 

further metal fragments to obtain so far unknown terminal metalloborylenes 6. 

Adding the transition metal base [Pt(PCy3)2] to 6 results in the formation of [{(η 5 -C5Me5) (CO)2Fe}(µ- 

B)(µ-H){CpW(CO)2}], showing an exceptional T-shaped coordination mode. Hence, this compound is 

best to be described as a metal-base stabilized metalloborylene. 

[1] P. Bissinger, H. Braunschweig, F. Seeler; Organometallics 2007, 26, 4700. H. Braunschweig, 

C. Kollann, K. W. Klinkhammer; Eur. J. Inorg. Chem. 1999, 9, 1523. 

[2] H. Braunschweig, K. Radacki, D. Scheschkewitz, G. R. Whittell; Angew. Chem. Int. Ed. 2005, 44, 

1658. 

[3] H. Braunschweig, I. Fernández, G. Frenking, K. Radacki, F. Seeler; Angew. Chem. 2007, 119, 5307.

Poster 5 

94 


Synthesis and Reactivity of Platinum Oxoboryl and Platinum Alkylideneboryl 

Complexes 

Johannes Brand, Holger Braunschweig, Krzysztof Radacki and Achim Schneider 

(johannes.brand@uni-wuerzburg.de) 



Until recently monomeric oxoboranes have been detected only as short-lived species in gas-phase [1] or 

low-temperature matrix experiments. [2] The reaction of Br 2 BOSiMe 3 with [Pt(PCy 3 ) 2 ] yielded the 

oxoboryl complex trans-[(Cy 3 P) 2 BrPt(B≡O)] via oxidative addition of a B−Br bond and spontaneous 

elimination of BrSiMe 3 . [3] 

Evidence for the remarkable stability of the oxoboryl ligand is demonstrated by its reaction with 

[Bu4N]SPh. The nucleophile does not react with the BO moiety but instead substitutes the ligand trans to 

the BO. [3] In contrast, abstraction of the bromide ligand with Ag[Al(pftb) 4 ] (pftb = perfluoro-tert-butoxy) 

induces instant cyclodimerization of the oxoboryl complex. [4] With Ag[BAr f 

4 ] (Arf = 3,5bis(trifluoromethyl)phenyl) 

and an excess of acetonitrile the cationic complex trans- 

[(Cy3P)2(MeCN)Pt(B≡O)][BAr f 

4 ] could be obtained.[5] With B(C6F5 ) 3 the oxoboryl complex yielded the 

Lewis acid-base adduct trans-[(Cy3P)2BrPt{B≡O B(C6F5 ) 3 }]. [5] Recently a 1,2-dipolar addition of 

Me3SiNCS to the oxoboryl moiety was also observed. [6] 

Analogously to the synthesis of the oxoboryl complex the reaction of Br2BCH(SiMe3 ) 2 with [Pt(PCy3 ) 2 ] 

yielded the first platinum alkylideneboryl complex trans-[(Cy3P) 2BrPt{B=C(H)SiMe3 }]. [6] In this 

complex the bromide ligand could be substituted with a methyl group by the reaction with methyllithium 

to obtain trans-[(Cy P) MePt{B=C(H)SiMe }]. Additionally the synthesis of the boryl complex trans- 

3 2 3 

[(Cy 3 P) 2 BrPt{B(Br)CH 2 SiMe 3 }] could be carried out via oxidative addition of one B�Br bond of 

Br 2 BCH 2 SiMe 3 to [Pt(PCy 3 ) 2 ]. However due to the lack of steric demand, no elimination of bromosilane 

was observed. 

[1] H. F. Bettinger, Organometallics 2007, 26, 6263–6267. 

[2] L. Andrews, T. R. Burkholder, J. Phys. Chem. 1991, 95, 8554–8560. 

[3] H. Braunschweig, K. Radacki, A. Schneider, Science 2010, 328, 345-347. 

[4] H. Braunschweig, K. Radacki, A. Schneider, Angew. Chem. Int. Ed. 2010, 49, 5993-5996. 

[5] H. Braunschweig, K. Radacki, A. Schneider, Chem. Commun. 2010, 46, 6473-6475. 

[6] J. Brand, Diploma thesis 2010, Julius-Maximilians-University Würzburg.

Poster 6 

95 


Novel Reactivity of Terminal Borylene Complex [Cp(CO)2Mn=B-tBu] 

Rong Shang, Holger Braunschweig and Krzysztof Radack 

(rong.shang@uni-wuerzburg.de) 



It has been shown that the reaction of the terminal borylene complex [Cp(CO)2Mn=B�tBu] (1) with 

platinum and palladium(0) complexes [M’(PCy3)2] (M’ = Pt, Pd) results in formation of heterodinuclear 

complexes [Cp(CO)Mn(μ-CO){μ-B(tBu)}M’(PCy3)2], [1] in a similar fashion to those reported for the 

Group 6 metal borylene complexes [(OC)5M=BN(SiMe3)2] (M = Cr, W). [2] Furthermore, complex 1 

undergoes metathesis reactions with polarized unsaturated substrates, such as benzophenone, to form 

exotic manganese carbene complexes via a [2+2] cycloaddition/cycloreversion mechanism. [3] 

Recent studies revealed vastly different behavior of 1 with seemingly similar substrates. The reaction 

with [AuClL] (L = PCy3, PPh3, ITol, ITol = [Tol-NCH]2C:) results in formation of heterodinuclear 

complexes [Cp(CO)2Mn(AuL){B(tBu)(Cl)}] (2), which are best viewed as products of 1,2-addition of the 

Au−Cl bond across the Mn=B bond. Furthermore, addition of two equivalents of super mesityl isonitrile 

(CNMes*, Mes* = 2,4,6-tri(tert)butylphenyl) to 1 induces coupling between its borylene moiety and the 

carbonyl ligands to form complex 3, which features a 11 B NMR shift of −57 ppm. Upon treatment with a 

strong Lewis acid, complex 3 converts back to the terminal borylene complex 1 quantitatively. Also, 

treatment of 2 with two equivalents of CNMes* results in loss of of AuClL and formation of 3. 

[1] H. Braunschweig, M. Burzler, T. Kupfer, K. Radacki and F. Seeler, Angew. Chem. Int. Ed. 2007, 46, 

7785–7787. 

[2] (a) H. Braunschweig, D. Rais and K. Uttinger, Angew. Chem. Int. Ed. 2005, 44, 3763-3766. 

(b) H. Braunschweig, K. Radacki, D. Rais and K. Uttinger, Organometallics 2006, 25, 5159-5164. 

[3] H. Braunschweig, M. Burzler, T. Kupfer, K. Radacki and F. Seeler, Angew. Chem. Int. Ed. 2007, 46, 

8071-8073.

Poster 7 

Stable Radicals from π-Conjugated Boroles 

96 


Holger Braunschweig and Christian Hörl 

(christian.hoerl@uni-wuerzburg.de) 

Institut of Inorganic Chemistry, Julius-Maximilians-Universität Wuerzburg, Am Hubland, 97074 

Wuerzburg, Germany 

Owing to their isoelectronic relationship to neutral methyl radicals, stable boron-radicals anions [BR3] • ˉ 

have attracted considerable attention. The most prominent representative is the trimesitylborane radical 

anion which has been investigated since the 1950s and characterized as a fairly stable species. [1] Stable 

boron diradicals have been studied to a lesser extent and only a few examples have been reported. 

Boroles are known for their strong electron deficiency and their antiaromaticity due to the 4π electron 

system. [4] In addition, boroles exhibit interesting spectroscopic properties which arise from the small 

HOMO-LUMO gap. Our group showed recently, that a stepwise reduction of boroles to their dianions is 

possible. Even the isolation of an unusual borole radical anion, bearing 5π electrons, was successful. [5] 

Starting from the thiophene bridged bisborole 1 we were able to isolate a stable borole-based diradical 

dianion 2. Herein we wish to present the structure and properties of the diradical 2. 

[1] H. C. Brown, V. H. Dodson, J. Am. Chem. Soc. 1957, 79, 2302. 

[2] D. Scheschkewitz, H. Amii, H. Gornitzka, W. W. Schoeller, D. Bourissou, G. Bertrand, Science 2002, 

295, 1880. 

[3] A. Racja, S. Racja, S. R. Desai, J. Am. Chem. Soc. 1995, 1957. 

[4] H. Braunschweig, T. Kupfer, Chem. Comm. 2011, 47, 10903. 

[5] H. Braunschweig, V. Dyakonov, J. O. C. Jimenez-Halla, K. Kraft, I. Krummenacher, K. Radacki, A. 

Sperlich, J. Wahler, Angew. Chem. Int. Ed. 2012, 51, 2977. 

[2, 3]

Poster 8 

97 


Synthesis and Characterisation of N-heterocyclic carbene adducts of P(I) 

cations 

Ala Swidan, Jennifer Nguyen, Bobby D. Ellis and Charles L.B. Macdonald 

(swidan@uwindsor.ca, cmacd@uwindsor.ca) 

Department of Chemistry and Biochemistry 

University of Windsor 

Our research group have long been interested in the synthesis of compounds containing low-valent main 

group elements. [1] Our recent progress toward the preparation of dye-like molecules that incorporate 

phosphorus in its +1 oxidation state (P I ) stabilized by N-heterocyclic carbenes (NHCs) is reported. Our 

group previously reported several approaches to the synthesis of base-stabilized univalent phosphorus 

halide reagents containing cations such as [(dppe)P] + . [2] Furthermore, we discovered that the reaction of 

two equivalents of many NHCs with such P I salts produces salts containing [(NHC)2P] + cations (Figure 1) 

through a ligand replacement mechanism in which the weaker phosphine ligands are displaced by the 

stronger NHC donors. [3] The structures, properties and reactivities of these molecules is detailed. 

[1] Ellis, B. D.; Macdonald, C. L. B., Coordination Chemistry Reviews, 2007, 251, 936-973. 

[2] Ellis, B. D.; Macdonald, C. L. B. Inorg. Chem. 2006, 45, 6864-6874. 

[3] Ellis, B. D.; Dyker, C. A.; Decken, A.; Macdonald, C. L. B. Chem. Commun. 2005, 1965-1967.

Poster 9 

98 


Formation and Reactivity of Intramolecular Ti-C Bond in Substituted 

Titanocene Derivatives 

Michal Horáček and Karel Mach 

(michal.horacek@jh-inst.cas.cz) 

J. Heyrovský Institute of Physical Chemistry of Academy of Sciences of the Czech Republic,v.v.i., 

Dolejškova 2155/3, 182 23, Prague 8, Czech Republic 

The paramagnetic singly tucked-in permethyltitanocene [Ti(III){η 5 :η 1 -C5Me4(CH2)}(η 5 -C5Me5)] (1) was 

first observed when an equilibrium mixture of decamethyltitanocene [Ti(η 5 -C5Me5)2] with its singly 

tucked-in hydride [TiH{η 6 -C5Me4(CH2)}(η 5 -C5Me5)] was sublimed under vacuum. [1] Later on, 

thermolysis of the decamethyltitanocene monoalkyl compounds [Ti(III)R(η 5 -C5Me5)2] (R = Me, Et, Pr, 

CH2CMe3) appeared to be another clean and convenient method for obtaining 1. [2] 

This contribution reports on the formation of intramolecular Ti-C bond in variously substituted titanocene 

derivatives and reactivity of the singly tucked-in permethyltitanocene 1 towards the series of various 

molecules. Particularly, the protolysis with hydrogen sulphide, silanols or alcohols opened an access to 

new titanocene sulphide compounds [3] or permethyltitanocene silanolates and alcoholates [4] , respectively. 

[1] J. E Bercaw, J. Am. Chem. Soc. 1974, 96, 5087. 

[2] G. A Luinstra, J. H Teuben, J. Am. Chem. Soc. 1992, 114, 3361. 

[3] J. Pinkas, I. Císařová, M. Horáček, J. Kubišta, K. Mach, Organometallics 2011, 30, 1034. 

[4] V. Varga, I. Císařová, R. Gyepes, M. Horáček, J. Kubišta, K. Mach, Organometallics 2009, 8(6), 

1748. M. Horáček, R. Gyepes, I. Císařová, J. Kubišta, J. Pinkas, K. Mach, J. Organomet. Chem. 

2010, 695, 2338. R. Gyepes, V. Varga, M. Horáček, J. Kubišta, J. Pinkas, K. Mach, Organometallics 

2010, 29, 3780.

Poster 10 

99 


Catalytic Trimerisation of Bissilylated Diazomethane and Aminoisonitrile 

Alexander Villinger, a Muhammad Ibad, a Peter Langer, a,b Fabian Reiß a and Axel Schulz a,b 

(alexander.villinger@uni-rostock.de) 

a Department of Chemistry, University of Rostock, Albert-Einstein Str. 3a, D-18059 Rostock, Germany; b 

Leibniz Institute for Catalysis at the University of Rostock, Albert-Einstein Str. 29a, D-18059 Rostock, 

Germany 

The silylium ion [Me3Si] + might be regarded as a sterically demanding big proton, and, similar to a 

proton, the bulky silylium ion is always solvated forming the [Me3Si(solv.)] + ion. [1] Only recently, the full 

series of salts containing the bissilylated halonium/pseudohalonium cations [Me3Si–X–SiMe3] + (X = F, 

Cl, Br, and I; CN, N3, OCN, SCN) were generated and fully characterized using the super Lewis acidic 

silylating media Me3Si–X and [Me3Si(solv.)] + salt. [2] In view of the success of the pseudohalogen concept in 

super Lewis acidic silylating media, we were intrigued by the idea to utilize the enormous Lewis acidity 

of the [Me3Si] + ion, to activate small molecules, such as bissilylated diazomethane (Me3Si)2CNN, which 

can be considered as a pseudochalkogen. In the present study, the three constitutional isomers with a 

NNC unit, (Me3Si)2CNN, (Me3Si)2NNC and (Me3Si)NCN(SiMe3) were reacted with 

[Me3Si(solv.)][B(C6F5)4] (solv. = HSiMe3, toluene) to afford the silylated pseudochalkogen salts. However, 

while the aminonitrilium cation [Me3SiNCN(SiMe3)2] + was obtained as colourless crystals, a more 

complex reaction was observed for the diazomethane and aminoisonitrile derivates, finally yielding the 

silylated 4-diazenyl-3-hydrazinyl-1H-pyrazole (1) which can be considered the formal trimerization 

product (Figure 1). Nevertheless, in both reactions, the [Me3SiCNN(SiMe3)2] + salt (2) could be identified 

as catalyst which crystallized out at the end of the reactions and indicated an isomerization of 

diazomethane to aminoisonitrile. The catalytic process can be carried out with catalyst concentrations less 

than 1 mole% and is completely selective. 

Figure 1. ORTEP drawing of the molecular structure of 1 and 2 in the crystal. 

[1] J. B. Lambert, S. Zhang, S. M. Ciro, Organomet. 1994, 13, 2430–2443; b) J. B. Lambert, S. Zhang, 

J. Chem. Soc., Chem. Commun. 1993, 383–384; C. A. Reed, Z. Xie, R. Bau, A. Benesi, Science 

1993, 262, 402–404. 

[2] M. Lehmann, A. Schulz, and A. Villinger, Angew. Chem. Int. Ed., 2009, 48, 7444–7447; A. Schulz, 

A. Villinger, Chemistry – Eur. J. 2010, 16, 7276–7281.

100 


Metallation of Cyclotetrasilyldiphosphin with Earthalkaline Silazanides 

Michael Feierabend and Carsten von Hänisch 

(michael.feierabend@chemie.uni-marburg.de) 

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4 

35032 Marburg, Germany 

In recent studies, we were able to synthesise the branched oligosilan tris(di-isopropyl-chlorosilyl)phenylsilan 

1. In a reaction of 1 with [Li(DME)PH2], the cyclic tetrasilyldiphospin 2 can be isolated, 

which is the result of a rearrangement of one of the di-isopropyl-silyl-groups. 

In this poster, we present the synthesis and characterization of 1 and 2 as well as the metallation of 

compound 2 with alkaline earth metal silazanides. 

The product of these reactions were characterised by multi nuclear NMR spectroscopy and single crystal 

X-ray structure analysis. They show a different degree of oligomerization depending on the metal used. 

SiiPr 2 

Cl 

Si 

SiiPr 2 

SiiPr 2 

Cl 

[Li(DME)PH 2] 

SiH 

Cl 

1 2 

M = alkaline earth metal 

Poster 11 

Si 

iPr 2 

PH 

Si 

iPr 2 

Si 

iPr 2 

PH 

M{N(SiMe 3) 2} 2

101 


Synthesis and Coordination Chemistry of Cagelike Siloxane Compounds of 

Elements of the 15th Group 

Christian Bimbös and Carsten von Hänisch 

(Bimboes@students.uni-marburg.de) 

Fachbereich Chemie, Philipps-Universität Marburg, Hans Meerwein-Straße 4, 35032 Marburg, Germany 

Recently, we reported the synthesis of the cage like compound P2[{SiMe2}2O]3 and its coordination 

properties. Further investigations on the coordination within the cage compound showed a dimerisation to 

the larger compound P4[{SiMe2}2O]6 after treating with the lithium salt of the weakly coordinating anion 

Li[Al{OC(CF3)3}4]. [1] 

On this poster, we report about the synthesis of the analogous arsenic and stibane compounds 

E2[{SiMe2}2O]3 (with E = As, Sb). The arsenic cage compound 1 was obtained by the reaction of 

Li[(dme)AsH2] with the dichlorodisiloxane (ClSiMe2)2O. We were able to obtain the complex 2 by the 

reaction of the arsenic cage compound As2[{SiMe2}2O]3 with a strong lewis acid AlEt3. On treating the 

arsenic cage compound As2[{SiMe2}2O]3 (1) with the lithium salt of the weakly coordinating anion 

Li[Al{OC(CF3)3}4], a dimerisation reaction to As4[{SiMe2}2O]6 (3) was observed similar to the 

corresponding phosphoric compound. Further it was possible to obtain the analogous Sb cage compound 

Sb2[{SiMe2}2O]3 (3) by the reaction of Na3Sb with the dichlorodisiloxane (ClSiMe2)2O. 

6 [Li(dme)AsH 2] + 3 O(SiMe 2Cl) 2 

2 Na 3Sb + 3 O(SiMe 2Cl) 2 

- 4 AsH 3 

- 6 LiCl 

- 6 NaCl 

Et 3Al 

Poster 12 

Me2Si O 

SiMe2 As O As 

1. Li[Al{OC(CF3) 3} 4] 

2. THF 

SiMe2 SiMe2 SiMe2 O 

1 

SiMe2 Me2Si SiMe2 O 

As O As 


2 

SiMe2 Me2Si SiMe2 O 

Sb O Sb 


4 

SiMe2 AlEt 3 

Me 2Si 

O 

Me 2Si 

As 

O 

Me 2 

Si 

O 

Me 2 

Si 

SiMe 2 

Me2Si As O 

Si 

Me2 Si 

Me2 

As 

SiMe2 O 

3 

SiMe2 [1] C. von Hänisch, F. Weigend, O. Hampe, S. Stahl, Chem. Eur. J. 2009, 15, 9642. 

As SiMe 2 

O 

SiMe 2

Poster 13 

102 


Generation of Tellurenyl Cation Species (RTe + ): Structures and Properties 

of Tellurophenium Salts 

Koh Sugamata, Takahiro Sasamori and Norihiro Tokoitoh 

(sugamata@boc.kuicr.kyoto-u.ac.jp) 

Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan 

Tellurenyl cations, RTe + , have attracted much attention for a long time. However, only a few stable 

examples are known due to their difficulty to isolate because of their intrinsic high reactivity. Although a 

tellurenyl cation derivative, [2,6-(Me2NCH2)2C6H3Te] + PF6 – , stabilized by intramolecular coordination of 

amino group was reported, no structural feature has been disclosed. [1] On the other hand, methyl- or 4fluorophenyl-substituted 

ditelluride was reported to be oxidized by a nitrosonium salt giving the 

corresponding transient species of tellurenyl cation. [2] In recent studies, the synthesis of an aryltellurenyl 

cation stabilized by the coordination of NHC was reported by Beckmann. [3] We expected that the 

chemical trapping products of low-coordinated tellurenyl cation species can be kinetically stabilized by a 

bulky aryl group such as Bbt group (see Figure). The dehalogenation reactions of Bbt-substituted 

tellurium halides [4] are rational to postulate the formation of a tellurenyl cation species as an 

intermediate. [5] In this presentation, we present the successful trapping reactions of a tellurenyl cation 

species with butadienes to give the corresponding 2,5-dihydrotellurophenium salts as stable colorless 

compounds. The re-generation of the tellurenyl cation species by its thermal retro[1+4]cycloaddition will 

also be described. 

[1] H. Fujihara, H. Mima, N. Furukawa, J. Am. Chem. Soc. 1995, 117, 10153. 

[2] C. Kollemann, F. Sladky, J. Organomet. Chem. 1990, 396, C1. 

[3] J. Beckmann, P. Finke, S. Heitz, M. Hesse, Eur. J. Inorg. Chem. 2008, 1921. 

[4] a) T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, Y. Furukawa, M. Kimura, S. Nagase, N. Tokitoh, 

Bull. Chem. Soc. Jpn. 2002, 75, 661; b) T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, N. Tokitoh, 

Chem. Lett. 2001, 42. 

[5] a) T. Sasamori, K. Sugamata, N. Tokitoh, Heteroatom Chem. 2011, 22, 405; b) K. Sugamata, T. 

Sasamori, N. Tokitoh, Chem. Asian J. 2011, 6, 2301. [6] K. Sugamata, T. Sasamori, N. Tokitoh, Eur. 

J. Inorg. Chem. 2011, 5, 775.

103 


Mechanistic Insights into the Formation of Phosphorus-Containing 

Ruthenacycles 

K. Morrow a , L. Rosenberg a , D. Pantazis b and R. McDonald c 

(kmorrow@uvic.ca) 

a) University of Victoria, Department of Chemistry, 

b) Max Plank Institute for Bioinorganic Chemistry 

c) University of Alberta, X-Ray Crystallography Department 

Phosphorus-containing metallacycles formed from the overall [2+2]-cycloaddition of terminal alkenes at 

a Ru-P π-bond [1] show promise as possible intermediates relevant to catalytic hydrophosphination. We 

have investigated the formation of these complexes in detail. In confirmation of DFT predictions, we have 

directly observed an η 2 -alkene adduct as an intermediate in the [2+2] cycloaddition. We have also 

demonstrated, through the construction of a Hammett plot showing non-linearity, that the mechanism of 

ruthenacycle formation is dependent on alkene substituent electronics. The formation of these 

phosphorus-containing ruthenacycles may occur via a more stepwise mechanism for electron-deficient 

alkenes as opposed to the concerted [2+2] cycloaddition of electron-rich alkenes. 

Ph3P Ru 

+ 

PCy2 R 

Ph 3P 

Ru 

HC CH2 R 

PCy 2 

Poster 14 

Ph3P H 

Ru R 

+ 

PCy2 Ph3P R 

Ru 

syn anti 

[1] Derrah, E. J.; Pantazis, D. A.; McDonald, R.; Rosenberg, L. Angew. Chem., Int. Ed. 2010, 49, 3367. 

H 

PCy 2

Poster 15 

104 


Functionalized Tris(pyrazolyl)borate and Tris(pyrazolyl)borate ligands as 

Potential PARACEST MRI Contrast Agents 

Emma Nicholls-Allison and David Berg 

(ecna@uvic.ca) 

Department of Chemistry, University of Victoria, Victoria, BC, Canada 

Traditional MRI contrast agents employ high dosages of gadolinium containing chelates in order to 

generate a suitable image in situ. However, toxicity concerns and depleting resources of the gadolinium 

metal have promoted studies into a new type of contrast agent utilizing a PARACEST mechanism. The 

crucial features of the ligand design are strong ligand-metal binding, exchangeable protons on the 

periphery, and water solubility. It is with these features in mind that we are studying both the 

tris(pyrazolyl)borate and tris(triazolyl)borate ligand systems. By installing a chelating group at the three 

position, the borate ligand can act as a hexacoordinate system, thus decreasing the ligand-metal lability. 

By introducing novel, functionalized groups at the three position, exchangeable protons can be introduced 

in order both participate in the PARACEST mechanism and increase the water solubility. Thus far, the 

coordination chemistry of a variety of novel, chelating tris(pyrazolyl)borate ligands has been studied.

Poster 16 

Synthesis of 1,2:3,4-Bis(ferrocene-1,1’-diyl)tetragermetane and its 

Photochemical Reaction 

Hisashi Miyamoto, Takahiro Sasamori and Norihiro Tokitoh 

(miyamoto@boc.kuicr.kyoto-u.ac.jp) 

Institute for Chemical Research, Kyoto University, Japan 

105 


There has been much interest in intramolecular electronic interaction between transition metals (delectrons) 

through an organic π-electron conjugated system. [1] On the other hand, double-bond 

compounds between heavier group 14 elements are known to exhibit higher HOMO and lower LUMO 

levels relative to those in olefins. We have already reported the synthesis and properties of 1,2bis(ferrocenyl)digermene 

as a novel d-π conjugated system. [2] Recently, we have shifted our attention 

towards the synthesis of 1,2-ferrocene-1,1’-diyldigermene 1. Attempted reductive ring-closing reactions 

of 1,1’-bis(dibromogermyl)ferrocene 3 resulted in the formation of the dimer of digermene 1, 1,2:3,4bis(ferrocene-1,1’-diyl)tetragermetane 

2 as a stable crystalline compound. We would like to report herein 

the detailed synthesis and photochemical reactivity of tetragermetane 2. 

When tetragermetane 2 was exposed to photo-irradiation from a medium pressure Hg lamp in benzene at 

room temperature, trigermirane 4 was exclusively obtained. Photochemical reactions of 2 in the presence 

of trapping reagents such as methanol and triethylsilane will also be described. 

ORTEP drawing of 2 (left) and 4 (right) at 30% probability. 

Hydrogen atoms and i-Pr groups are omitted for clarity. 

[1] Demadis, K. D.; Hartshorn, C. M.; Meyer, T. J. Chem. Rev. 2001, 101, 2655. 

[2] Sasamori, T.; Miyamoto, H.; Sakai, H.; Furukawa, Y.; Tokitoh, N. Organometallics 2012, 31, 3904.

Poster 17 

106 


Unexpected Formation of Novel 1,2,3-Tri-substituted 1H-2,1-Benzazaboroles 

by Amidolithiation of Dichloroboro-substituted N,C-Chelating Ligands 

Martin Hejda a , Antonín Lyčka b , Roman Jambor a , Aleš Růžička a and Libor Dostál a* 

(libor.dostal@upce.cz) 

a Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of 

Pardubice, Studentská 573, Pardubice CZ-532 10, Czech Republic, 

b Research Institute for Organic Syntheses, Rybitví 296, CZ-533 54 Pardubice, Czech Republic 

An attempt to prepare precursors of intramolecularly coordinated boramidinates [1] (top of Fig. 1) 

containing N,C-chelating ligands via nucleophilic substitution of chlorine atoms by lithium anilides led, in 

one step and good yields, to unexpected and unprecedented formation of B-N heterocyclic compounds: 

novel 1,2,3-tri-substituted 1H-2,1-benzazaborols (bottom of Fig. 1). These structures are rare; only a few 

1H-2,1-benzazaboroles substituted in the positions 1,2 and 3 are known [2] . However, these already known 

1H-2,1-benzazaboroles are generally accessible by more complicated reaction protocols. Furthermore, the 

observed compounds contain two NH functionalities, which may be deprotonized and used as reactants 

for further reactions. Depending on the temperature and the stoichiometry used in the studied reactions, 

the substitution of two anilide groups can be directed to either 1,3- or 1,2- positions of benzazaborole 

cycle (bottom of Fig. 1). The hot results extending this topic will be presented and discussed. 

Figure 1 

The authors thank the Grant Agency of the Czech Republic for financial support (Projects No. 

P207/10/0130 and P207/12/0223). 

[1] C. Fedorchuk, M. Copsey, T. Chivers, Coord. Chem. Rev. 2007, 251, 897-924. 

[2] (a) A. Rydzewska, K. Ślepokura, T. Lis, P. Kafarski, P. Młynartz, Tetrahedron Lett. 2009, 50, 132- 

134. (b) A. M. Genaev, S. M. Nagy, G. E. Salnikov, V. G. Shubin, Chem. Commun. 2000, 1587- 

1588.

Synthesis of Heteroboroxines of 14 and 15 Group Elements 

107 


Barbora Mairychová, Tomáš Svoboda, Roman Jambor and Libor Dostál 

(roman.jambor@upce.cz) 


Pardubice, Studentská 573, Pardubice CZ-532 10, Czech Republic 

Boroxines are well known species, easily accessible by dehydration of the corresponding organoboronic 

acids. [1] In 2005, Yaghi and coworkers reported on the synthesis and characterization of the first 

crystalline boroxine covalent organic framework (COF). [2] Since the disclosure of this COF many COFrelated 

materials emerged, which significantly expanded the interest in material properties of boroxines. 

The chemistry of heteroboroxines, in which one of the boron atom is substituted by a heteroatom M to 

form a MB2O3 six-membered ring, remains nearly unexplored despite of an extensive research in the 

field. [2] As the result of our investigation of main group organometallic compounds, [3] we report herein a 

straightforward synthetic strategy for the synthesis of unprecedented heteroboroxines LM[(OBR)2O] and 

L(Ph)Sn[(OBR)2O], where M = Sb and Bi, L = [2,6-bis(dimethylamino)methyl]phenyl, R = Ph, 4- 

CF3C6H4 and ferrocenyl), comprising the MB2O3 six membered rings (Figure 1). 

NMe 2 

= L 

NMe 2 

Poster 18 

R 

O 

L 

M 

O 

B O B 

R 

R 

L Ph 

Sn 

O O 

B B 

O 

R M 

Ph Sb: 1a Bi: 2a 3a 

4-CF 3 C 6 H 4 Sb: 1b Bi: 2b 3b 

1-ferrocenyl Sb: 1c Bi: 2c 3c 

Figure 1 

The authors wish to thank the Grant agency of the Czech Republic project no. P106/10/0443. 

[1] D. G. Hall, G. C. Frye, in Boronic Acids, WILEY-VCH, Weinheim, 2005. 

[2] (a) X. Ma, Z. Yang, X. Wang, H. W. Roesky, F. Wu, H. Zhu, Inorg. Chem. 2011, 50, 2010-2014; (b) 

Z. Yang, X. Ma, R.B. Oswald, H. W. Roesky, M. Noltemeyer, J. Am. Chem. Soc. 2006, 128, 12406- 

12407. 

[3] (a) P. Šimon, F. de Proft, R. Jambor, A. Růžička, L. Dostál, Angew. Chem. Int. Ed. 2010, 49, 5468. (b) 

M. Bouška, L. Dostál, A. Růžička, L. Beneš, R. Jambor, Chem. Eur. J. 2011, 17, 450. (c) M. Bouška, 

L. Dostál, F. de Proft, A. Růžička, A. Lyčka, R. Jambor, Chem. Eur. J. 2011, 17, 455. (d) M. Bouška, 

L. Dostál, Z. Padělková, A. Lyčka, S. Herres-Pawlis, K. Jurkschat, R. Jambor, Angew. Chem. Int. Ed. 

2012, 51, 3478. 

R

Poster 19 

108 


Organometallic Group 14 And 15 Chalcogenides and Phenylchalcogenides 

Marek Bouška, Petr Šimon, Roman Jambor, Antonín Lyčka and Libor Dostál 

(libor.dostal@upce.cz) 


Pardubice, Studentská 573, Pardubice CZ-532 10, Czech Republic, Research Institute for Organic 

Syntheses, Rybitví 296, CZ-533 54 Pardubice, Czech Republic 

We have recently demonstrated that using of NCN chelating, so called pincer type, ligands allowed 

isolation of several group 14 and 15 element molecular chalcogenides (E = S, Se, Te), that in some cases 

contain unprecedented terminal M-E bonds or unprecedented ring systems such as M(µ-S5)M or MS4. [1] 

These compounds were prepared either by oxidative addition of elemental chalcogens to low valent metal 

precursors or by the reaction of the parent organometallic chlorides with alkali metal chalcogenides Li2E 

(E = S, Se, Te). As a part of our ongoing interest in the group 14 and 15 element chalcogenides, we are 

also interested in preparation of group 15 chalcogenides kinetically stabilized by a bulky ligand (Fig. 1) or 

in corresponding arylchalcogenides synthesized by the oxidation of low valent precursors, especially 

tin(I), antimony(I) and bismuth(I) compounds, with diaryldichalcogenides (Fig. 1). The fresh results 

targeting these two targets will be presented and discussed. 

Figure 1 

The authors wish to thank the Grant agency of the Czech Republic project no. P207/10/0130. 

[1] (a) P. Šimon, F. de Proft, R. Jambor, A. Růžička, L. Dostál, Angew. Chem. Int. Ed. 2010, 49, 5468. 

(b) L. Dostál, R. Jambor, A. Růžička, A. Lyčka, J. Brus, F. de Proft, Organometallics 2008, 27, 6059. 

(c) L. Dostál, R. Jambor, A. Růžička, R. Jirásko, V. Lochař, L. Beneš, F. de Proft, Inorg. Chem. 

2009, 48, 10495. (d) M. Bouška, L. Dostál, A. Růžička, L. Beneš, R. Jambor, Chem. Eur. J. 2011, 17, 

450. (e) M. Bouška, L. Dostál, F. de Proft, A. Růžička, A. Lyčka, R. Jambor, Chem. Eur. J. 2011, 17, 

455. (f) P. Šimon, R. Jambor, A. Růžička, A. Lyčka F. de Proft, L. Dostál, Dalton Trans. 2012, 41, 

5140. (g) M. Bouška, L. Dostál, Z. Padělková, A. Lyčka, S. Herres-Pawlis, K. Jurkschat, R. Jambor, 

Angew. Chem. Int. Ed. 2012, 51, 3478.

Poster 20 

109 


New Applications of Woollins’ Reagent for the Synthesis of Small 

Organoselenium Heterocycles to Macro Phosphorus/Selenium Heterocycles 

Guoxiong Hua, Junyi Du, Rebecca A. M. Randall, Alexandra M. Z. Slawin and J. Derek Woollins 

(gh15@st-andrews.ac.uk) 

School of Chemistry, University of St Andrews, Fife, KY16 9ST, UK 

2,4-Bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide [{PhP(Se)(µ-Se)}2], Woollins’ Reagent, WR, a 

selenium analogue of the well-known Lawesson’s Reagent (2,4-bis(p-methoxyphenyl)-1,3dithioadiphosphetane-2,4-disulfide, 

LR), has less unpleasant chemical properties and can be prepared 

readily and safely handled. [1] Now it is commercial available in the Sigma-Aldrich catalogue (No: 

572543). WR has been becoming a very useful selenium source or building block in synthetic chemistry 

in recent years. [2] In this poster, we demonstrate its new reactivities towards the organic substituents. 

Refluxing a mixture of equimolar amount of WR and cyanamides in toluene, followed by quenching with 

water led to the formation of phenethylselenoureas, the latter were treated with equimolar ArCOCH2X 

giving a series of 4-aryl-N-alkyl-N-phenethyl-1,3-selenazol-2-amines in excellent yields; meanwhile, 

reacting WR with an equivalent of disodium alkyldiols, followed by ring-closure treatment with 

appropriate dihaloalkanes resulted in the corresponding nine- to fifteen-membered phosphorus-selenium 

heterocycles in medium to good yields. 

[1] P. Gray, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins, Chem. Eur. J. 2005, 11, 6221. 

[2] (a) A. Rothenberger, W. Shi, M. Shafaei-Fallah, Chem. Eur. J. 2007, 13, 5974. (b) P. Amaladass, N. 

S. Kumar, A. K. Mohanakrishnan, Tetrahedron 2008, 64, 7992. (c) G. Hua, J. D. Woollins, Angew. 

Chem. Int. Ed. 2009, 48, 1368. (d) G. Hua, J. B. Henry, Y. Li, A. R. Mount, A. M. Z. Slawin, J. D. 

Woollins, Org. Biomol. Chem. 2010, 8, 1655. (e) G. Hua, J. M. Griffin, S. E. Ashbroom, A. M. Z. 

Slawin, J. D. Woollins, Angew. Chem. Int. Ed. 2011, 50, 4123. (f) G. Hua, A. M. Z. Slawin, J. D. 

Woollins, Synlett 2012, 23, 1170. (g) J. A. Gómez Castaño, R. M. Romano, H. Beckers, H. Willner, 

C. O. Della Védova, Inorg. Chem. 2012, 51(4), 2608.

110 


Unexpected Dehalogenation Reactions of Dichloroborane Bearing a NCN- 

Pincer Ligand 

Masaichi Saito, a Kaori Matsumoto a and Mao Minoura b 

(masaichi@chem.saitama-u.ac.jp) 



b Department of Chemistry, School of Science, Kitasato University, Kitasato, Sagamihara, Kanagawa, 

228-8555, Japan 

The synthesis of cationic and anionic boron species is of considerable interest from the viewpoint of 

fundamental curiosity and their potential usefulness as ligands and catalysts. In the course of our studies 

on the synthesis of dianionic species of main group elements, [1] we became interested in the synthesis of 

dicationic and dianionic boron species that have the same carbon ligands on the boron atoms. We then 

chose 2,6-bis[(diisopropylamino)methyl]- phenyl group, an NCN-pincer ligand, as a protecting group on 

the reactive boron center, which is utilized to stabilize reactive species of Group 13 elements. [2] We report 

herein the synthesis of novel dichloroborane 1 bearing an NCN-pincer ligand, which reacts with AgBF4 in 

the absence and the presence of pyridine to afford unexpected borenium salt 2 and difluoroborane 3, 

respectively. Reduction of 1 is also demonstrated. 

2,6-Bis[(diisopropylamino)methyl]phenyllithium 4 reacted with trichloroborane etherate to afford 

dichloroarylborane 1. Reaction of 1 with AgBF4, however, afforded an unexpected product, borenium salt 

2. In the presence of pyridine, difluoroborane 3 was obtained. The formation of 2 and 3 suggests the 

generation of intermediary boron dication 5. 

iPr2N Br NiPr2 tBuLi Et2O AgBF4 (2 equiv.) 

CH2Cl2, r. t. 

AgBF 4 (2 equiv.) 

pyridine 

CH 2Cl 2, r. t. 

iPr2N Ni N 

Pr2 i iPr2N Pr 

Li Li 2 

i Pr2N 

F 

4 

B 

O 

B 

2 

F 

N i Pr 2 

iPr2N B NiPr2 3 

Poster 21 

F 2 

BCl 3-OEt 2 

iPr2N B NiPr2 [1] For a review, see: Saito, M. Coord. Chem. Rev. 2012, 256, 627. 

[2] (a) Contreras, L.; Cowley, A. H.; Gabbaï, F. P.; Jones, R. A.; Carrano, C. J.; Bond M. R. J. 

Organomet. Chem. 1995, 489, C1. (b) Schlengerann, R.; Sieler, J.; Hey-Hawkins, E. Main Group 

Chem. 1997, 2, 141. (c) Dostál, L.; Jambor, R.; Růžička, A.; Jirásko, R.; Císařová, I.; Holeček, J. J. 

Organomet. Chem. 2006, 691, 35. 

+ 

BF 4 − 

Cl 

5 

1 

Cl 

iPr2N B NiPr2 2+

Poster 22 

Studies on Platinum Complexes of 1,8-Naphthosultone and 1,8- 

Naphthosultam 

111 


Louise M. Diamond, Fergus R. Knight, Alexandra M. Z. Slawin and J. Derek Woollins 

(ld397@st-andrews.ac.uk) 

School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, Scotland, UK 

In the late 1970’s and early 1980’s Teo and co-workers [1] coordinated tetrathionaphthalene (TTN), 

tetrachlorotetrathionaphthalene (TCTTN) and tetrathiotetracene (TTT) to a Pt(PPh3)2 motif through an 

oxidative addition reaction with [Pt(PPh3)4]. We [2] have used this oxidative reaction to study the 

coordination chemistry of 1, 8-dichalcogen naphthalenes and the oxidised derivatives of naphtho [1,8-cd] 

1,2-dithiole, to platinum bisphosphines. 

Here, a series of platinum bisphosphine complexes bearing 1,8-naphthosultone as a bidentate ligand have 

been prepared. An analogous reaction was studied with 1,8-naphthosultam. However, it was found that 

1,8-naphthosultam acts as a monodentate ligand. Thus, for example, reaction of 1,8-naphthosultone with 

[PtCl2(PPh3)2] gives [Pt(1-(SO2),8-(O)-nap)(PPh3)2] (1) whereas reaction of 1,8-naphthosultam with 

[PtCl2(PPh3)2] gives [Pt(1-(SO2),8-(N)-nap)(PPh3)(Cl)] (2). 

Figure. X-ray crystal structures of complexes (1) and (2) with hydrogen atoms omitted for clarity 

Further studies into more electron rich peri substituted systems will also be reported. 

[1] B. K. Teo, F. Wudl, J. H. Marshall and A. Krugger, J. Am. Chem. Soc., 1977, 99, 2349; B. K. Teo, P. 

A. Snyder-Robinson, Inorg. Chem., 1978, 17, 3489; B. K. Teo, P. A. Snyder-Robinson, Inorg. 

Chem., 1979, 18, 1490; B. K. Teo, P. A. Snyder-Robinson, Inorg. Chem., 1981, 20, 4235. 

[2] S. M. Aucott, H. L. Milton, S. D. Robertson, A. M. Z. Slawin, G. D. Walker and J. D. Woollins, 

Chem. Eur. J., 2004, 10, 1666.

Activation of White Phosphorus 

Laura Forfar, Nicholas Norman and Chris Russell 

(laura.forfar@bristol.ac.uk) 

School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK 

112 


The activation of white phosphorus is a topic of current interest and seeks to find a more sustainable and 

environmentally friendly route into the production of organophosphorus compounds which have uses in 

the food, agricultural and pharmaceutical industries. This can be done by early transition metals, late 

transition metals and main group elements and compounds. 

In this work we sought to activate white phosphorus using the group 11 metals. We achieved this by 

reaction of equimolar amounts of simple inorganic salts, MX (M = Au, Cu, X = Cl; M = Ag, X = OTf) 

with a Lewis acid (GaCl3) and P4 in a CH2Cl2 solution. 31 P NMR spectroscopy showed a downfield shift 

in all cases, being more pronounced for Au (-452) than for Cu (-499) and Ag (-513 ppm). In the solid 

state, the compounds showed remarkably different structures. Cu and Ag formed coordination polymers 

based on P4MGaCl4 in ion-contacted structures. For copper, Cu + , GaCl4 and P4 units are all involved in 

the central framework forming the first example of a coordination polymer where P4 is an integral part of 

the bonding network. For silver, Ag + and GaCl4 - units are linked through bridging chloride ligands to form 

a ladder structure with each Ag bonded η 2 - to a P4 unit. 

Cu 

P 

P 

P 

P 

For gold, different chemistry resulting in an ion-separated structure is observed. [Au(η 2 -P4)2] + cations ionseparated 

from [GaCl4] - anions form the first homoleptic P4 complex of gold. [1] This complex, predicted to 

be the most stable homoleptic group 11 cation of the type [(η 2 -P4)2M] + is the final member of the series to 

be found. [2] 

Ga 

Cu 

Cl 

Cl 

P 

Cl 

P 

P 

Ga 

P 

Poster 23 

P 

Cl 

Au 

P 

P 

[1] Forfar, L; Clark, T; Green, M; Mansell, S; Russell, C; Sanguramath, R; Slattery, J, Chem Commun, 

2012¸ 48, 1970 

[2] a) Krossing, I; J. Am. Chem. Soc., 2001, 123, 4603 b) Santiso-Quiñones, G; Reisinger, A; Slattery, J; 

Krossing, I, Chem Commun, 2007, 5046 

Cl 

Ga 

P 

Cl 

P 

Cl 

Cl Ga 

Ag 

Cl 

P 

P 

P 

Cl

Poster 24 

113 


Novel P,N Cage Ligands via Rearrangement of Azaphosphiridine Complexes 

José Manuel Villalba Franco and Rainer Streubel 

(villalba@uni-bonn.de) 

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn 

Gerhard-Domagk Str. 1, 53121 Bonn, Germany 

2H-Azaphosphirene [1] and azaphosphiridine [2] complexes were reported first by Streubel and co-workers. 

The former have provided access to various P,N- and P,O-cage ligands via thermally induced 

rearrangements. [3] Very recently, new derivatives of azaphosphiridine complexes were synthesized via 

reaction of a transient Li/Cl phosphinidenoid complex (route i) or a thermally generated terminal 

phosphinidene complex (route ii) and N-methyl C-aryl imines. [4] Here, we report on generation and 

rearrangements of labile P-Cp* substituted azaphosphiridine complex 4a,b that lead to two novel type of 

P,N cage complexes 5a,b and 6a,b. The 31 P NMR spectroscopic reaction monitoring for route i in the b 

case, showed transient P-Cp* aza-phosphiridine complex 4b at low temperature which undergoes rapid 

isomerisation to com-plex 5b. Under thermal conditions the formation of the novel P-N cage complexes 

6a-b was observed. Further studies revealed a unique equilibrium between both cage-type ligands. [5] 

NMR data as well as X-ray structures of the new complexes will be reported. 

[1] R. Streubel, Coord. Chem. Rev. 2002, 227, 175-192. 

[2] R. Streubel, A. Ostrowski, H. Wilkens, F. Ruthe, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl. 

1997, 36, 378-381. 

[3] a) R. Streubel, U. Schiemann, N. Hoffmann, Y. Schiemann, P. G. Jones, D. Gudat, Organometallics 

2000, 19, 475-481 ; b) M. Bode, G. Schnakenburg, P. G. Jones, R. Streubel, Organometallics, 2008, 

27, 2664-2667. 

[4] a) S. Fankel, H. Helten, G. von Frantzius, G. Schnakenburg, J. Daniels, V. Chu, C. Müller, R. 

Streubel. Dalton Trans. 2010, 39, 3472-3481; b) R. Streubel, J. M. Villalba Franco, G. 

Schnakenburg, A. Espinosa Ferao, Chem. Commun., 2012,48, 5986-5988. 

[5] J.M. Villalba Franco, A. Espinosa, G. Schnakenburg, R. Streubel, manuscript in preparation.

114 


Role of Non-Innocent Pyridine Ligands in the Isolation of Unprecedented 

Ge(0) and Sn(0) Complexes 

Johanna Flock, Amra Suljanovic, Ana Torvisco, Michaela Flock and Roland C. Fischer 

(johanna.flock@tugraz.at) 

Institut für Anorganische Chemie, TU-Graz, Stremayrgasse 9, A-8010 Graz, Austria 

Recently, a novel type of Group 14 compounds has been developed, where the Group 14 elements are in 

the formal oxidation state of zero. [1] Group 14 elements in an formal oxidation state of zero are found in 

compounds where, for example, the E=E core (E= Si 2 , Ge 3 ) is coordinated by two Lewis base carbene 

ligands. Other examples of formal E(0) species are “non classical” allenes R2E=E’=ER2 (E, E’= C, Si, Ge, 

Sn). [2] However, in literature no example of a neutral mononuclear compound is reported where a heavier 

main group atom is stabilized by only one donor molecule in an oxidation state of zero. 

Herein, we report neutral and mononuclear Ge 0 (1a) and Sn 0 (1b) complexes, which are stabilized by the 

DIMPY ligand, a Ge 0 complex (2) stabilized by MIMPY (2-[ArN=C(H or Me)](NC5H3) (Ar= C6H3-2,6iPr2)) 

[3] and further low valent Sn II species, as a MeDIMPYSn II (3) (Figure 1). The experimental results 

were also supplied by theoretical studies. The DIMPY ligand (2,6-[ArN=C(H)]2(NC5H3) (Ar= C6H3-2,6i 

Pr2) had previously been employed in the synthesis of highly reactive main group element complexes in 

low oxidation states, which are exclusively cationic. [3] The particular property of these ligands is the fact 

that these are non-innocent ligands and undergo electron-transfer reactions. [4] 

The Synthetic pathways, spectroscopic and structural features as well as computational results of these 

Ge 0 , Sn 0 and Sn II complexes will be discussed. 

N2 

N3 

Sn 

(1b) 

N1 

C1 

C2 

Poster 25 

N1 

N2 

Ge 

(2) (3) 

Figure 1.: Crystal structure of Sn(0) di(imino)pyridine complex (1b), the Sn(I) chloride 

di(imino)pyridine complex (2b) (L= 2,6-[DippN=C(H or Me)]2(NC5H3)) and the aromatic germylene (3) 

(L= 2-[DippN=C(H or Me)](NC5H3)). 

[1] Martin D., Soleilhavoup M., Bertrand G. Chem. Sci. 2011, 2, 389-399. 

[2] (a) Tonner R., Frenking G. Angew. Chem., Int. Ed 2007, 46, 8695-9698. (b) Tonner R., Frenking G. 

Chem. Eur. J. 2010, 16, 10160 – 10170. (c) Dyker C. A., Lavallo V., Donnadieu B., Bertrand G. 

Angew. Chem. Int. Ed. 2008, 47, 3206 –3209. (d) Ishida S., Iwamoto T., Kabuto C., Kira M., Nature, 

2003, 421, 725-727. (e) Wiberg N., Lerner H. W., Vasisht S. K., Wagner S., Karaghioso K., Nöth H., 

Ponikwar W. Eur. J. Inorg. Chem. 1999, 1211-1218 

[3] (a) Benko, Z.; Burck, S.; Gudat, D.; Nieger, M.; Nyulaszi, L.; Shore, N., Dalton Trans. 2008, 4937- 

4945. (b) D. L. Reger, T. D. Wright, M. D. Smith, A. L. Rheingold, S. Kassel, T. Concolino, B. 

Rhagitan, Polyhedron 2002, 21, 1795-1807. 

[4] a) Martin C. D., Ragogna P. J., Dalton Trans. 2011, 11976-11980. b) Ragogna, P. J., J. Am. Chem. 

Soc. 2009, 131, 15126-15127; Reeske, G.; Cowley, A. H., Chem. Commun. 2006, 1784-1786. c) 

Baker, R. J.; Jones, C.; Kloth, M.; Mills, D. P., New. J. Chem. 2004, 28, 207-213. d) Ullah, F.; Oprea, 

A. I.; Kindermann, M. K.; Bajor, G.; Veszpremi, T.; Heinicke, J., J. Organom. Chem., 2009, 694, 397- 

403. 

N2 

Si 

N3 

Sn 

N1

115 


Cyclization of Low Valent Main Group 3 and 4 Element Compounds 

Petra Wilfling, 

Stefan Müller, Michaela Flock and Roland C. Fischer 

(petra.wilfling@tugraz.at) 

Institut für Anorganische Chemie, TU Graz, Stremayrgasse 9/IV, 8010 Graz, Austria 

A significant approach towards the synthesis of main group element compounds in unusual oxidation 

states is the use of sterically demanding ligands, particularly of terphenyl systems. [1] Among the various 

kinds of compounds containing main group 4 elements in unusual oxidation states, molecules including 

heavier elements in aromatic systems take an especially interesting position due to their rareness. [2] 

This presentation will mainly focus on the synthetic routes towards cyclic and aromatic Ge containing 

compounds stabilized by terphenyl ligands as well as their heavier analogues (see figure 1). Furthermore, 

the synthesis of metalloid Ga clusters [3] , which are outstanding due to their exceptional intermediate state 

between elemental metal and molecular compound [4] , will be discussed. Characterization of the products 

was performed employing spectroscopic (multinuclear NMR, UV-Vis, X-ray diffraction) and 

computational methods. Experimental and computational trends concerning structures, stabilities, NMR 

shifts and UV-Vis spectra but also chemical reactivity will be presented. 

Figure 1: 

Poster 26 

Cyclization of precursors containing heavier group 4 elements, obtained by conversion of terphenyl 

stabilized tetrylenes with phosphaalkynes . 

[1] see e.g.: Rivard, E.; Power, P.P. Inorg. Chem. 2007, 32, 10047-10064. 

[2] see e.g.: Tokitoh, N. Acc. Chem. Res. 2004, 37, 86-94. 

[3] Wilfling, P.; Fischer, R.C. unpublished results. 

[4] Driess, M.; Nöth, H. Molecular Clusters of the Main Group Elements, 1st ed.; Wiley- VCH: 

Weinheim, 2004.

Poster 27 

116 


Toward Connection of Ruthenium Complexes to Tin/Sulfur Clusters. 

Eliza ter Jung and Stefanie Dehnen 

(Jungel@students.uni-marburg.de) 

Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Straße, 

D-35043 Marburg, Germany 

In recent years, the design of ruthenium complexes has attracted great interest due to their properties, 

which are useful for diverse applications: the utilization of Ru(II) complexes ranges from dye-sensitized 

solar cells [1] and chromophores [2] to water oxidation [3] , for instance. Many of these complexes include Ndonor-, 

chelating ligands like terpyridines. [1] In our group, we have developed the ligands of organotetrelchalcogenide 

cages, especially a double-decker-like RSn/S cluster and an adamantane-like RGe/S cluster, 

both of which are based on an inorganic Tt4S6 core (Tt = tetrel), to make the organic shell reactive toward 

further functionalization. Starting out from a keto-functionalized ligand R = CMe2CH2COMe, reactions 

with hydrazines, hydrazones or hydrazides have been successful (scheme 1). [4] 

Scheme 1: Core-Rearrangement and/or functionalization of the double-decker-like cage [(RSn)4S6] (R = 

CMe2CH2COMe) with phenylhydrazine (left) or hydrazine (right), respectively. 

To combine the versatile properties of the inorganic cluster core with the potentially applicable properties 

of Ru(II) complexes, one of our current aims is to attach these to an Sn/S cage. This can be achieved 

following different ways, either by functionalization of the Sn/S cluster with a suitable donor ligand and 

subsequent Ru(II) semi-sequestration, or by attachment of one of the ligands of a pre-formed Ru(II) 

complex to the cluster. So far, it was possible to connect a bipyridyl ligand to the cluster via an azine 

bond. This precursor is currently tested in reactions with coordinatively unsaturated Ru(II) complexes, 

according to the first synthetic route (scheme 2). 

Scheme 2: Conversion of a donor-functionalized Sn/S precursor with a Ru(II) complex. 

[1] P. G. Bomben, T. J. Gordon, E. Schott, C. P. Berlinguette, Angew. Chem. 2011, 123, 10870-10873. [2] 

K. C. D. Robson, C. P. Berlinguette et al., Inorg. Chem. 2011, 50, 5494-5508. [3] B. Radaram, X. Zhao et 

al., Inorg. Chem. 2011, 50, 10564-10571. [4] Z. Hassanzadeh Fard, L. Xiong, C. Müller, M. Holynska, S. 

Dehnen, Chem. Eur. J. 2009, 15, 6595-6604.

Poster 28 

117 


An Efficient Approach to Ternary Intermetalloid Clusters: 

Reactions of Binary Zintl Anions with Transition Metal Complexes 

Bastian Weinert, Rodica Ababei and Stefanie Dehnen 

(Weinertb@students.uni-marburg.de) 

Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Straße, D-35043 Marburg, 

Germany 

Intermetalloid clusters, [1] which combine main group (semi-)metals with transition metal clusters, belong 

to the most recent developments in the field of Zintl anion chemistry and physics. [2] So far, the clusters 

have usually been obtained by reacting solutions of Zintl phases A4Tt9 or A3Pn7 (A: alkali metal, Tt: 

tetrel, Pn: pnictogen), which comprise homoatomic anions, in liquid NH3 or en/[2.2.2]crypt with 

transition metal compounds. However, due to a relatively high charge, most of the phases with molecular 

tetrel polyanions, e.g. A4Tt4, show poor solubility, [3] which has complicated reactions of further species. 

To overcome this problem, and to add another degree of freedom regarding the electron number of the 

resulting clusters, we recently extended this approach by using binary Zintl anions with a combination of 

Group 14/15 elements as well-soluble precursors, namely [Sn2Sb2] 2− , [Sn2Bi2] 2− , with only 2− charge 

according to the Zintl-Klemm-Busmann [4] pseudo element concept. This has led to the generation of a 

large variety of ternary anions such as [Pd3@Sn8Bi6] 4– , [Ln@Sn7Bi7] 4− and [Ln@Sn4Bi9] 4− (Ln = La, 

Ce). [5,6] Our current investigations again extent this field by transferring our approach to the employment 

of pseudo-homoatomic precursors [Sn2Sb2] 2− [7] and [Pb2Bi2] 2− , and to the Group 13/15 element 

combination [GaBi3] 2− and [InBi3] 2− . [8] Here, we present first results of this variation that indicate the 

subtle influence of charges, atomic radii and Lewis basicities of the involved elements. Isostructural 

element substitutions were observed in [Zn@Zn5Pb3Bi3@Bi5] 4– , [Ni2@Pb7Bi5] 3– , [Ln@Pb7Bi7] 4− and 

[Ln@Pb4Bi9] 4− . Interestingly with Ln = La, Ce, Nd, we also obtained clusters with novel structures or 

different charges, {[La@In2Bi11](µ-Bi)2[La@In2Bi11]} 6− or [La@Sn6Sb8] 3– . Besides characterization of 

the compounds, our studies include formation mechanisms and electronic structures of the uncommon 

intermetalloid cages. 

[1] T. F. Fässler, S. D. Hoffmann, Angew. Chem. Int. Ed. 2004, 43, 6242; [2] S. Scharfe, F. Kraus, S. 

Stegmaier, A. Schier, T. F. Fässler Angew. Chem. Int. Ed. 2011, 50, 3630; [3] M. Waibel, F. Kraus, S. 

Scharfe, B. Wahl, T. F. Fässler, Angew. Chem. Int. Ed. 2010, 49, 6611; [4] W. Klemm, E. Busmann, Z. 

Anorg. Allg. Chem. 1963, 319, 297; [5] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 

14168; [6] F. Lips, M. Hołyńska, R. Clerac, U. Linne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, 

J. Am. Chem. Soc. 2012, 134, 1181; [7] F. Lips, I. Schellenberg, R. Pöttgen, S. Dehnen, Chem. Eur. 

J. 2009, 15, 12968; [8] L. Xu, S. C. Sevov, Inorg. Chem. 2000, 39, 5383.

Poster 29 

118 


Synthesis of Alumosilicates with Lanthanides and the Influence of Anagostic 

Interactions on the Conformation of their Rings 

Vojtech Jancik, * Kimberly Thompson Montero, Marisol Reyes Lezama 

(vjancik@unam.mx) 

Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carr. Toluca Atlacomulco km. 

14.5, C.P. 50200, Toluca, Estado de México, México. *Academic staff from the Universidad Nacional 


A two-step synthesis from easily accessible precursors (AlMe3, ( t BuO)2Si(OH)2 and Cp3Ln) leads to a 

facile formation of alumolsilicates with lanthanides containing a central 4R alumosilicate ring. [1] This ring 

is fused with two four-membered lanthanidosilicate rings to form a centrosymmetric molecule. The 

conformation of the molecules depends on the metal covalent radii and the presence and number of the 

anagostic interactions. These interactions are formed between one of the methyl groups of the AlMe2 unit 

and the lanthanide metal. 

Figure 1. Molecular structure of the alumosilicate with gadolinium, comparison of the three different ring 

conformations and the deviation of the methyl group from the ideal orientation towards the aluminum 

atom. Thermal ellipsoids at 50 % probability only for noncarbon atoms. Hydrogen atoms have been 

omitted for clarity. 

[1] Kimberly Thompson Montero, Marisol Reyes Lezama, Vojtech Jancik, manuscript en preparation.

Poster 30 

119 


Tin Aminoalkoxides and their Platinum Complexes: Structural Diversity and 

Catalytic Activity in Polymerisation Reactions 

T. Zöller, C. Dietz, L. Iovkova-Berends and K. Jurkschat 

(thomas.zoeller@tu-dortmund.de) 

Lehrstuhl für Anorganische Chemie II der Technischen Universität Dortmund, 

Otto-Hahn-Str. 6, 44227 Dortmund, Germany 

In cooperation with Bayer Material Science we found an excellent latent catalytic activity in polyurethane 

synthesis of inorganic tin compounds based on amino alcohol ligands. [1] Prominent representatives of 

these tin(II) and tin(IV) derivates are 2,8-dioxa-5-aza-1-stannabicyclo[3.3.0]octanes of the types 

R 1 N(CH2CR 2 2O)2Sn and R 1 N(CH2CR 2 2O)2SnX2 (R = alkyl, Ph, Me2NCH2CH2, MeOCH2CH2; X = 

halogen, alkoxide etc.). These non-toxic compounds hold great potential to replace the commonly used 

mercury-based catalysts. A systematic variation of the substituents X and R allows controlling the switchtemperature 

of the catalysts but gives also access to great structural diversity. 

The tin aminoalkoxides are suitable to stabilize molecular tin(II) compounds such as tin(II) chloride oxide 

(1). Reactions with platinum complexes give unusual tin platinum clusters such as 2. The tin(II) 

compounds may act as σ-donor ligands, insert into Pt–Cl bonds or take part in rearrangement reactions. 

We also report enantiopure tin aminoalkoxides that hold potential for asymmetric induction in catalytic 

processes. [2] 

[1] J. Krause, S. Reiter, S. Lindner, A. Schmidt, K. Jurkschat, M. Schürmann, G. Bradtmöller, 

DE 102008021980, 2008. 

[2] (a) T. Zöller, L. Iovkova-Berends, T. Berends, C. Dietz, G. Bradtmöller, K. Jurkschat, Inorg. Chem. 

2011, 50, 8645. (b) T. Zöller, L. Iovkova-Berends, C. Dietz, T. Berends, K. Jurkschat, Chem. Eur. J. 

2011, 17, 2361. (c) K. Jurkschat, M. Schürmann, T. Zöller, L. Iovkova-Berends, DE 102010012237, 

2010. (d) T. Zöller, C. Dietz, L. Iovkova-Berends, O. Karsten, G. Bradtmöller, A.-K. Wiegand, Y. 

Wang, V. Jouikov, K. Jurkschat, Inorg. Chem. 2012, 51, 1041.

Poster 31 

Tellurium-Containing Heterocycles Stabilized by P2N2 Rings 

120 


Andreas Nordheider †‡ , Tristram Chivers ‡ , Thirumoorthi Ramalingam, ‡ Ignacio Vargas-Baca # , Alexandra 

M. Z. Slawin † and J. Derek Woollins † 

(an349@st-andrews.ac.uk) 

† University of St Andrews, Purdie Building, St Andrews, KY16 9ST, Scotland, UK 

‡ University of Calgary, Calgary, AB T2N 1N4, Canada 

# McMaster University, Hamilton, L8S 4M1, Canada 

Recently, we decribed a mild oxidative approach to generate the trimeric macrocycles [P2N2(µ-E–E–)]3 (E 

= S, Se) with a planar P6E6 framework in which dichalcogenido (–E–E–) groups are linked by 

perpendicular P (V) 2N2 rings. [1] This poster presents the results of the application of this approach to 

tellurium derivatives, [2] which provide important insights into the initial oxidation process, as well as 

notable differences in the final outcome of the oxidation compared to that observed for sulfur- or 

selenium-containing systems. Furthermore, we report metathetical reactions between the precursor 

dianion and various dihalides, which lead to a series of new heterocyclic tellurium compounds 

incorporating P2N2 rings. The products of these metatheses were characterized by multinuclear NMR 

spectroscopy ( 31 P, 77 Se, 125 Te NMR.) and, in some cases, by X-ray crystallography. 

Figure 1: Novel phosphorus-tellurium heterocycles (left: representative scheme, right: crystal structure of 

a cyclic phosphorus-tritelluride). 

These novel compounds provide an opportunity for an in-depth investigation of the chemical behavior 

and structural parameters of phosphorus-tellurium heterocycles. Furthermore, the compounds offer 

considerable scope for new phosphorus-tellurium chemistry. 

http://chemistry.st-andrews.ac.uk/staff/jdw/group/profjdwoollins.html 

[1] A. Nordheider, T. Chivers, R. Thirumoorthi, I. Vargas-Baca and J. D. Woollins, Chem. Commun., 

2012, 48, 6346. 

[2] G. G. Briand, T. Chivers and M. Parvez, Angew. Chem. Int. Ed., 2002, 41, 3468.

Poster 32 

Experimental and Computational Studies of the Oxidation and 

Chalcogenation of the 1,4-C2P4 Ring 

121 


P. J. W. Elder a , T. Chivers, a T. L. Roemmele b and R. T. Boeré b 

(chivers@ucalgary.ca) 

a Department of Chemistry, University of Calgary, Calgary AB, Canada 

b Department of Chemistry & Biochemistry, University of Lethbridge, Lethbridge AB, Canada 

The chemistry of cyclophosphanes (RP)n (R = alkyl, aryl n = 3-6) has been extensively investigated in 

terms of both their tendency to undergo insertion and rearrangements with chalcogens [1] and their 

electrochemical properties. [2] The closely related cyclocarbaphosphanes however, have been less well 

studied. While insertion reactions have been reported for the CP4 ring with both selenium and sulphur, 

the PCP moiety has been shown to remain intact. [1,3] By contrast with these systems, there have been no 

reports of the chemical and/or redox properties of the related C2P4 six-membered ring, 1. 

The tert-butyl derivative 1 (R = t Bu) is obtained in good yield from the reaction of 

Cl2PCH2PCl2 with four equivalents of t BuMgCl. Computational studies using DFT 

suggest a weak cross-ring P-P interaction for the radical cation of 1 (R = t Bu), and a 

bicyclic system for the corresponding dication. Cyclic voltammetry shows two wellseparated, 

but irreversible, waves at (a) 0.49 V (GC), 0.52 V (Pt) and (b) 1.08 V (GC), 1.16 V (Pt) in 

dichloromethane consistent with the formation of the mono- and di-cations. Experimental investigations 

of the oxidation of 1 (R = t Bu) and a comparison of the chemical reactivity toward chalcogens will be 

presented. 

[1] Review: G. Hua and J.D. Woollins, Angew. Chem. Int. Ed., 2009, 48, 1368. 

[2] H.-G. Schäfer, W. W. Schoeller, J. Niemann, W. Haug, T. Dabisch and E. Niecke, J. Am. Chem. 

Soc. 1986, 108, 7481. 

[3] (a) P. Kilian, A. M. Z. Slawin and J. D. Woollins, Chem. Commun., 2001, 2288; (b) P. Kilian P. 

Bhattacharyya, A. M. Z. Slawin and J. D. Woollins, Eur. J. Inorg. Chem., 2003, 1461.

Poster 33 

122 


Synthesis and Coordination Chemistry of Zwitterionic Pnictogen(I) Centers 

Jonathan W. Dube 1 , Charles L.B. Macdonald 2 and Paul J. Ragogna 1 

(jdube7@uwo.ca, pragogna@uwo.ca) 

1 Department of Chemistry and the Center for Materials and Biomaterials Research 

Western University, 1151 Richmond St, London, Ontario, N6A 5B7, Canada, 2 Department of Chemistry 

and Biochemistry, The University of Windsor, 401 Sunset Ave, Windsor, Ontario, N9B 3P4, Canada 

The recent developments of triphosphenium cations (1), [1] have focused on their convenient synthesis as 

opposed to their coordination chemistry. [2,3] This is surprising as they formally possess two lone pairs of 

electrons and are isoelectronic to the carbodiphosphorane, a compound well known to be a strong ligand. 

We have prepared and fully characterized a new class of zwitterionic Pn(I) (Pn = P, As) centers (2) 

utilizing the anionic bis(phosphino)borate ligand class developed by Peters et al. [4,5] Without the external 

counterion necessary for traditional triphosphenium cations, 2P has shown increased solubility in 

nonpolar solvents and enhanced Lewis basic behaviour when compared to 1. The unique coordination to 

gold (3) and rhodium (4) as well as calculations on these complexes will be discussed. 

[1] A. Schmidpeter, S. Lochschmidt, W.S. Sheldrick, Angew. Chem. Int. Ed. 1982, 21, 63. 

[2] B.D. Ellis, M. Carlesimo, C.L.B. Macdonald, Chem. Commun. 2003, 1946. 

[3] E.L. Norton, K.L.S. Szekely, J.W. Dube, P.G. Bomben, C.L.B. Macdonald, Inorg. Chem. 2008, 47, 

1196. 

[4] J.C. Thomas, J.C. Peters, J. Am. Chem. Soc. 2001, 123, 5100. 5) J.C. Thomas, J.C. Peters, Inorg. 

Chem. 2003, 42, 5055.

Poster 34 

Stannylphosphonium Salts 

123 


E. P. MacDonald, a L. Doyle, a S. Chitnis, b N. Burford, b * U. Werner-Zwanziger a and A. Decken c 

(lizmac@dal.ca) 

a 

Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada 

b 

Department of Chemistry, University of Victoria, Victoria, BC, V8W 3V6, Canada 

c 

Department of Chemistry, University of New Brunswick, Fredericton, NB, E3A 6E2, Canada 

The first examples of stannylphosphonium salts have been prepared as coordination complexes of 

stannylium cations with phosphine ligands. Synthetic procedures involve activation of a Sn _ Cl bond by 

chloride ion abstraction promote donation from the phosphine, and by virtue of the cationic charge the 

Sn _ P interaction is enhanced. Examples of complexes include tin centers that adopt, tetracoordinate and 

pentacoordinate geometries, and cations can be mono or dicationic. 

Stannylphosphonium (I and II) and stannyldiphosphonium cations (III and IV). 

[1] MacDonald, E.; Doyle, L.; Burford, N.; Werner-Zwanziger, U.; Decken, A. Angew. Chem. Int. Ed., 

2011, 50, 11474-11477.

Poster 35 

124 


Functionalized Tin-Sulfur Clusters: Synthesis, Characterization and 

Investigations of the Formation Pathway 

Jens P. Eußner and Stefanie Dehnen 

(jens.eussner@chemie.uni-marburg.de) 

Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße, 


Organic-inorganic hybrid materials attract attention in current research for a variety of different reasons. 

Inorganic building units linked by organic substituents show very interesting chemical and physical 

properties, that are different from those of the single components alone − well known from metal-organic 

frameworks. Organic decorated clusters (RT)xEy (T = Si, Ge, Sn; E = O, S, Se, Te) represent the basic 

building units, aiming at the extension into even more versatile multinary clusters as inorganic nodes, 

potential applications and hybrid networks. Recent work of our group describe the synthesis, 

characterization and derivatization of various binary clusters with functionalized ligands R, terminated by 

reactive groups like C=O or COOH. [1−3] According to Scheme 1, an organotin-trihalide furnishs the 

desired functionality of the clusters. To synthesize novel clusters with different functional groups, and to 

establish a library of according clusters, we generated organotetrel-trichlorides with alkene, alkyne and 

acid anhydride functional groups. These are to be transferred into the corresponding binary and multinary 

clusters, with a preliminary focus on T = Sn and E = S. Besides their chemical and physical properties, 

the formation and dynamics of functionalized clusters in solution is of interest. [4] By application of 

different reactants and reaction conditions, several intermediates could be observed and isolated. Based 

on this, we can propose the following route of condensation (Scheme 2). 

Scheme 1: Synthetic route into functionalized chalcogenidometallate clusters (R F = functional organic 

substituent; R x = functional molecule with complementary reactivity; T = Ge, Sn; X = Cl, Br, I; E = S, Se, 

Te; A = alkali metal, E = S, Se, Te, TMS). 

Scheme 2: Proposed formation pathway from an organotintrichloride through several intermediates to an 

according organotinsulfide cluster. 

[1] Z. Hassanzadeh Fard, L. Xiong, C. Muller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15, 6595- 

6604. [2] Z. Hassanzadeh Fard, R. Clerac, S. Dehnen, Chem. Eur. J. 2010, 16, 2050-2053. [3] Z. 

Hassanzadeh Fard, M. R. Halvagar, S. Dehnen, J. Am. Chem. Soc. 2010, 132, 2845-2849. [4] M. Bouška, 

L. Dostál, Z. Padělková, A. Lyčka, S. Herres-Pawlis, K. Jurkschat, R. Jambor, Angew. Chem. 2012, 124, 

3535-3540.

Poster 36 

125 


Silver(I) Coordination Complexes: Controlling Self-assembly in the 

Construction of Supramolecular Networks 

Fergus R. Knight, Rebecca A. M. Randall, Lucy Wakefield, Alexandra M. Z. Slawin and J. Derek 

Woollins 

(frk@st-andrews.ac.uk) 

EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, U.K 

Coordination chemistry is an integral feature of inorganic and bioinorganic chemistry, with many 

applications in polymer design and materials science. In recent times, the metal-ligand interaction has 

emerged as an important tool for the manufacture of supramolecular metal complexes and is prominent in 

the design of organic solids and metal-organic frameworks (MOFs). Crystal engineering utilises the 

metal-ligand coordination bond to construct coordination networks, generally through the self-assembly 

of tuneable building blocks. Bridging organic ligands acting as rigid supports are linked in an ordered 

lattice, building extended and often multidimensional networks with central metal ions. Self-assembly, 

which dictates the structural motif of the final complex is controlled by experimental conditions. Factors 

such as the central metal ion oxidation state, the coordination geometry, the metal-to-ligand ratio, the 

nature and spacer length of the bridging ligand, the presence of solvents and the type of counter-anions, 

all play a significant role. Silver has become a fashionable building block for connecting organic ligands 

in supramolecular networks. 

The series of chalcogen-donor ligands Acenap[EPh][E`Ph] (Acenap = acenaphthene-5,6-diyl; E/E` = S, 

Se, Te) 1 coupled with silver(I) salts provide ideal building blocks for constructing coordination networks 

due to the diversity of the silver coordination geometry and the contrasting donor functionalities of the 

rigid acenaphthene supports. Acenaphthene derivatives [Acenap(EPh)(E`Ph)] (Acenap = acenaphthene- 

5,6-diyl; E/E` = S, Se, Te) [1] were each independently treated with silver tetrafluoroborate [AgBF4] and 

silver trifluoromethanesulfonate [AgOTf]. The coordinating ability of the counter-anions, the type of 

donor atoms available to the silver(I) metal centre and the nature of the solvents used during the reaction 

and recrystallisation stages have a dramatic effect on the final solid state structure and leads to the 

formation of unusual coordination architectures; 3D supramolecular metal-organic frameworks, 1D 

extended helical chain polymers, mononuclear, monomeric, silver(I) sandwich complexes, threecoordinate 

monomeric, silver(I) complexes. [2] 

[1] L. K. Aschenbach, F. R. Knight, R. A. M. Randall, D. B. Cordes, A. Baggott, M. Bühl, A. M. Z. 

Slawin and J. D. Woollins, Dalton Trans., 2012, 41, 3141. 

[2] F. R. Knight, R. A. M. Randall, L. Wakefield, A. M. Z. Slawin and J. D. Woollins, Chem. Eur. J., 

submitted.

126 


Synthesis and Characterization of Chalcogenophosphonium Cations 

S.H. Lucas and N. Burford 

(shlucas@uvic.ca) 

Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada 

The Burford group has developed synthetic procedures to phosphinophosphonium [1] , 

pnictinopnictonium [2,3] , and stannylphosphonium cations [4] . An extension of this previous work involves 

the group 16 elements (the chalcogens, Ch), with the intention of applying high yield synthetic 

approaches to Ch-P bond formation giving thio, seleno, and tellurophosphonium cations. 

Through the use of chalcogen halides, and halide abstracting agents, chalcogen cations are generated in 

situ (Figure 1a), which then react with phosphines to form chalcohenophosphonium cations (Figure 1b). 

The chalcohenophosphonium cations are characterized using 31 P{ 1 H}, 1 H, 13 C{ 1 H}, 77 Se{ 1 H}, and 

125 Te{ 1 H} NMR spectroscopy and X-ray crystallography. 

a 

R Ch X + ABS Ch 

R Ch + ABSX - 

b 

H + 

+ PR' 3 

Poster 37 

R + ABSX - 

H + 

R 

Ch 

+ PR'3+ ABSX - 

Figure 1: Proposed synthetic approach for the formation of chalcohenophosphonium cations. a) Halide 

abstraction of RChX. b) Formation of chalcohenophosphonium cation. 

R, R′ = Alkyl, Aryl, ABS = Halide abstraction agent, X= F, Cl, Br 

[1] Dyker and Burford., Chem. Asian J., 2008, 3, 28. 

[2] Conrad, Burford, et al., J. Am. Chem. Soc., 2009, 131, 5066. 

[3] Chitnis, Peters, et al., Chem. Commun., 2011, 47, 12331. 

[4] Macdonald, Doyle, et al., Angew. Chem. Int. Ed., 2011, 50, 11474.

Poster 38 

Ge(I)-Ge(I) as a Building Unit to Construct Oligomeric Germanes 

Hsien-Chen Yu, Fan-Shan Yang and Yi-Chou Tsai 

(yictsai@mx.nthu.edu.tw) 

Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan 30013 

127 


Stabilized by sterically hindered ligands, the univalent germanium dimers of the type RGeGeR have been 

recognized, and they all exist in a trans-bent conformation. [1-3] Notably, the Ge(I)–Ge(I) bond order is in 

the range of 1-3. Herein, we report the employment of a terdentate 2,6-diamidopyridyl ligand to stabilize 

a Ge2 2+ motif and give an unprecedented cis-bent complex. The separation of the single bonded Ge–Ge is 

2.5168(6) Å. This dimeric germanium(I) species turns out to be a good synthon for the preparation of 

oligomeric germanes. For example, linear mixed-valent homotetranuclear Ge I 2Ge II 2 and mixed-valent 

heterotetranuclear Ge I 2Sn II 2 and Ge I 2Zn II 2 complexes can be prepared via salt metathesis. Furthermore, a 

bent trinuclear Ge II Ge III 2 and cyclic homo-divalent tetranuclear and pentanuclear germanes can also be 

prepared through redox reactions. 

[1] Stender, M.; Phillips, A. D.; Wright, R. J.; Power, P. P. Angew. Chem., Int. Ed. 2002, 41, 1785. 

[2] Sugijama, Y.; Sasamori, T.; Hosoi, Y.; Furukawa, Y.; Takagi, N.; Nagase, S.; Tokitoh, N. J. Am. 

Chem. Soc. 2006, 128, 1023. 

[3] Green, S. P.; Jones, C.; Junk, P. C.; Lippert, K.-A.; Stasch, A. Chem. Commun. 2006, 3978.

128 


Synthesis and Structures of Titanastannene Coordinated by a Stannylene and 

Ti2Sn4 Ring Compound 

Takuya Kuwabara, a Masaichi Saito, a Jing Dong Guo b and Shigeru Nagase b 

(s11ds003@mail.saitama-u.ac.jp) 



b Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho, Sakyou-ku, 

Kyoto, 606-8103, Japan 

Heavier congeners of the cyclopentadienyl anion have received much attention in view of their 

aromaticity. [1] Our group has succeeded in the synthesis of dilithio-stannole [2] and –plumbole [3] and 

concluded that they have considerable aromatic character, based on the X-ray analyses, NMR studies and 

theoretical calculations. We next investigate the reactions of dilithiostannole with various metal reagents 

to obtain stannole complexes 

Reactions of dilithiostannole 1 [4] with Cp2TiCl2 followed by recrystallization provided two different 

crystals, one of which is dark purple and diamagnetic, and the other of which is dark red and 

paramagnetic. X-ray diffraction analysis revealed that the products are titanastannene complex 2 and 

compound 3 bearing a Ti2Sn4 six-membered ring with sandwich structures. The Ti−Sn bond lengths in 2 

are 2.6860(17) and 2.7255(18) Å, which are much shorter than those in 3 (2.9080(11), 2.9245(10) Å) and 

the Ti−Sn bond lengths ever reported (2.842−2.984 Å). In the 119 Sn NMR of 2, a sharp signal was 

observed at 1332.5 ppm, which indicates that the tin atoms have stannylene character. Theoretical 

calculations revealed that the Ti−Sn bond is a double bond consisting of σ-donation of a stannylene 

moiety to the Ti center and back-donation from d(Ti) to p(Sn). Interestingly, a unique interaction between 

the two p orbitals on the tin atoms is also found. 

Li(Et2O) Et Et 

Sn 

Et 

Et 

Li 

1 

Cp 

Cp 

Ti 

Sn 

Sn 

2 

Poster 39 

[1] For example of recent reviews, see: (a) Saito, M.; Yoshioka, M. Coord. Chem. Rev. 2005, 249, 765. 

(b) Lee, V. Y.; Sekiguchi, A. Angew. Chem., Int. Ed. 2007, 46, 6596. (c) Lee, V. Y.; Sekiguchi, A. In 

Organometallic Compounds of Low-coordinate Si, Ge, Sn and Pb, Wiley, Chichester, p335. (d) 

Saito, M. Coord. Chem. Rev. 2012, 256, 627. 

[2] Saito, M.; Haga, R.; Yoshioka, M.; Ishimura, K.; Nagase, S. Angew. Chem., Int. Ed. 2005, 44, 6553. 

[3] Saito, M.; Sakaguchi, M.; Tajima, T.; Ishimura, K.; Nagase, S.; Hada, M. Science 2010, 328, 339. 

[4] Saito, M.; Kuwabara, T.; Kambayashi, C.; Yoshioka, M.; Ishimura, K. Nagase, S. Chem. Lett. 2010, 

39, 700. 

Li 

Sn 

Sn 

Cp 

Ti 

Cp 

Cp 

Ti 

Cp 

3 

Sn 

Sn 

Li

129 


Weak Te,Te Bonding Through the Looking Glass of NMR Spin-Spin Coupling 

Michael Bühl, a Fergus Knight, a Anezka Krístková, b Olga L. Malkina b and J. Derek Woollins a 

(jdw3@st-andrews.ac.uk) 

a EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 

9ST, UK 

b Slovak Academy of Sciences, Institute of Inorganic Chemistry, SK-84536 Bratislava, Slovakia 

NMR spin-spin coupling between two nuclei can be a probe for the chemical bonding between them. The 

"through-space" coupling between formally nonbonded atoms can be assessed computationally. [1] Pnictogen 

and chalgocen substituents, placed in peripositions on a naphthalene scaffold (Chart I), show onset of multicentre 

bonding. [2] To explore possible relationships between these two aspects, we now report a joint DFT and 

experimental study of J(Te,Te) couplings in peri-napthalene ditellurides. 

Chart I 

Poster 40 

Huge "across-the bay" Te,Te couplings in the kHz range have been predicted computationally at 

appropriate levels of DFT (ZORA-SO), and have been confirmed experimentally for N1 and A1. These 

couplings turn out to be strongly dependent on the molecular conformation and can be related to the spatial 

overlap of lone-pair orbitals (assessed through the coupling deformation density pathway [1] ) and the onset of 

multicentre bonding (through natural bond orbital analysis). J(Te,Te) couplings can thus be a sensitive probe 

("looking glass") into electronic and geometrical structure of ditellurides. 

[1] O. L. Malkina, A. Kristkova, E. Malkin, S. Komorovsky, V. G. Malkin, Phys. Chem. Chem. Phys. 

2011, 13, 16015. 

[2] L. K. Aschenbach, F. R. Knight, R. A. M. Randall, D. B. Cordes, A. Baggott, M. Bühl, A. M. Z. 

Slawin, J. D. Woollins, Dalton Trans. 2012, 41, 3141.

Poster 41 

130 


Mono- and Binuclear Organoindium Thiolate Complexes and their Reactivity 

as Catalysts in Lactone Polymerization 

Glen G. Briand a , Jessica D. Marks a , Ryan G. Wareham a , Andreas Decken b , Laura E.N. Allen c and 

Michael P. Shaver c 

(gbriand@mta.ca) 

a Department of Chemistry and Biochemistry, Mount Allison University, Sackville NB Canada 

b Department of Chemistry, University of New Brunswick, Fredericton, NB Canada 

c Department of Chemistry, University of Prince Edward Island, Charlottetown, PE Canada 

Polylactides have been identified as possible candidates as alternative biodegradable and bio-renewable 

polymers (plastics) with specialized applications in the pharmaceutical and microelectronics industries 

(Dove et al. Chem. Soc. Rev. 2010, ). Ring opening polymerization (ROP) has been found to be a superior 

method for the preparation of these materials in that it allows for a greater degree of control over the 

molecular parameters of the resulting polymer, including lower polydispersities, higher molecular weights 

and higher end group fidelity. Recently, some compounds of indium have been shown to facilitate the 

ROP of both rac-lactide (Mehrkhodavandi et al. Angew. Chem., 2008; Tolman et al., J. Am. Chem. Soc., 

2010) and ε-caprolactone (Huang et al. Inorg. Chim. Acta, 2006), though there have been very few studies 

in this area. Indium based catalysts are attractive due to their new reactivity profile, low toxicity and 

stability in water. In this context, we have prepared a series of methylbis(thiolato)indium compounds 

containing bifunctional ester-, amine- and ether-thiolate ligands which exhibit mono- or binuclear 

structures. Their syntheses, structures and reactivity as ROP catalysts toward cyclic lactones will be 

discussed.

Poster 42 

131 


Synthesis of Selenium- and Tellurium-Containing Aminosilane Ligands 

Jamie S. Ritch 

(j.ritch@uwinnipeg.ca) 

Department of Chemistry, The University of Winnipeg, 515 Portage Avenue, Winnipeg, MB R3B 2E9 

Canada 

Materials featuring selenium or tellurium are of great contemporary interest as components in advanced 

electronic devices. Commercial examples include low-cost solar cells (CdTe), [1] and fast response IR 

detectors (PbSe). [2] While p-block and late d-block chalcogenides are generally well-studied, [3] there 

exists a great potential for development of novel Se- and Te-containing materials of the early and mid dblock 

elements. 

A new class of heavy chalcogen-containing ligand, 1, is being developed to enable the synthesis of CVD 

precursors to transition metal selenides and tellurides. This contribution will discuss the preparation of 

aminosilane ligands 1, and some preliminary studies of their coordination chemistry towards transition 

metals. 

[1] First Solar website. http://www.firstsolar.com/en/Innovation/CdTe-Technology (accessed June 13, 

2012). 

[2] Hamamatsu Photonics website. http://jp.hamamatsu.com/products/sensor-ssd/pd128/pd134/ 

index_en.html (accessed June 13, 2012). 

[3] See, for example: (a) Dey, S.; Jain, V. K. Platinum Metals Rev. 2004, 48, 16-29; (b) Bochmann, 

Chem. Vap. Deposition 1996, 2, 85-96.

Borane Catalyzed Post-polymerization Modification of Polysilanes 

132 


Peter T. K. Lee, Miranda K. Skjel and Lisa Rosenberg 

(peterlee@uvic.ca) 

Department of Chemistry, University of Victoria, P.O. Box 3065, Stn CSC Victoria, BC, V8W 3V6, 

Canada 

We previously reported the borane-catalysed chemoselective Si-H activation to make new Si-S containing 

oligosilanes. [1] We report here the catalytic post-polymerization modification of poly(phenylsilylene) by 

hydrosilation and heterodehydrocoupling reactions with thioketone and thiols, respectively, catalysed by 

B(C6F5)3. Three new random copolymers with up to 40% -SR sidechain incorporation were isolated and 

characterized by 1 H/ 13 C/ 29 Si NMR, IR, GPC, UV-Vis, and elemental analysis. Importantly, the borane 

catalyst is chemoselective for Si-H activation over Si-Si bond cleavage: no small molecular weight 

oligosilanes were detected by GC/MS or 1 H NMR, and an increase in molecular weight from the starting 

poly(phenylsilylene) to S-substituted polysilane was determined by light scattering GPC. These results 

along with recent efforts to extend the post-polymerization modification method to other organic 

substrates, such as chelating sidechains to make Si• radical recombination competitive with Si-Si chain 

scission, will be presented. 

5 mol % B(C 6F 5) 3 

HS-p-C6H4CH3 

-H2 

H 

Si 

Ph n' 

H S 

p-C6H4CH 3 

Si 

n 

Ph 

Si 

m 

Ph 

C 6 D 6 

J=188 Hz 

29 Si: 99 MHz 

1 H: 500 MHz 

DEPT90 

H-Si-S polymer endcaps 

Poster 43 

PhSiH 

PhSiH 

-10 -20 -30 -40 -50 -60 -70 

Figure: 29 Si DEPT NMR of Starting and S-modified Poly(phenylsilylene) 

[1] Harrison, D. J.; Edwards, D. R.; McDonald, R.; Rosenberg, L. Dalton Trans. 2008, 3401 

ppm

H2N 

N 

N N 

Poster 44 

133 


Networking of Semiconductor Clusters by Non-metal Linkage or Transition Metal 

Coordination 

Beatrix Barth and Stefanie Dehnen 

(barthb@students.uni-marburg.de) 

Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Straße, 


In the last decade, the design of metal-organic frameworks (MOFs) has attracted considerable attention in 

supramolecular and materials chemistry due to their enormous variety of interesting structural topologies 

and wide potential applications as functional materials. [1] In spite of the known and outstanding 

characteristics of chalcogenidometallate phases, the synthesis of chalcogenidometallate-organic 

frameworks is not studied extensively so far. [2] Our group recently investigated the synthesis and 

reactivity of new ω-carbonyl-functionalized thiostannate clusters of the general type [(R 1 Sn)4(µ-S)6] (with 

R 1 = CMe2CH2COMe in 1) [3] that possess good prerequisites to form chalcogenido-MOFs. The 

functionalized Sn/S cages not only enable an approach to a new class of hybrid materials; they also 

exhibit a suitable reactivity for non-metal linkage via hydrazine-functionalized organic units, such as 

realized at the synthesis of 2 (Scheme 1). [4] 

1 2 

Scheme 1: Synthesis of compound 2, consisting of [Sn6S10] units that are linked by 1,5-bis[(E)-2- 

(4-methylpentan-2-ylidene)hydrazinyl]naphthalene organic spacers. 

Consequently, there is a high interest in the further development of the synthetic pathways to interconnect 

these clusters not only by bis-, but also via tris- and tetra-functionalized organic units, such as hydrazinefunctionalized 

adamantanes. Another approach towards networks with chalcogenidometallate cages as 

nodes is accessible by choosing R 1 as a chelating ligand to form according clusters like 3. After cluster 

formation, the network will be formed by transition metal coordination. Precursors to these pathways 

have been synthesized. As an alternative, the metals can be incorporated in the metallate cages, such as 

observed at a reaction of 3 with Zn 2+ , thus producing new ternary systems like 4 that still provide donorligands 

for further metal coordination. [5] 

1 3 4 

Scheme 2: Introduction of a bidentate ligand and coordination and insertion of ZnX2 (X = Cl, Br, I) into 3. 

[1] J. L. C. Rowsell, O. M. Yaghi, Microp. Mesop. Mat. 2004, 73, 3. [2] S. Dehnen, M. Melullis, Coord. 

Chem. Rev. 2007, 251, 1259; X. Bu, N. Zheng, P. Feng, Chem. Eur. J. 2004, 10, 3356. [3] Z. H. Fard, L. 

Xiong, C. Müller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15, 6595. [4] Z. H. Fard, M. R. 

Halvagar, S. Dehnen, J. Am. Chem. Soc. 2010, 132, 2848. [5] B. Barth, E. ter Jung, S. Dehnen, in 

preparation. 

ZnX2 

X = Cl, Br, I

134 


Investigation of Redox Potentials of the Three-dimensional Aromatic 

Carborate Anions [1-R-CB11X5Y6] - (R = H, Me; X = H, Me, Hal, Y = H, Hal) 

Christoph Bolli a , Carsten Knapp a , René T. Boeré b , Maik Finze c , Alexander Himmelspach c and Tracey L. 

Roemmele b 

(cbolli@uni-wuppertal.de) 

a Fachbereich C - Anorganische Chemie, Bergische Universität Wuppertal 

Gaußstraße 20, 42119 Wuppertal, Germany 

b University of Lethbridge 

c Universität Würzburg 

Halogenated 1-carba-closo-dodecaborate anions are three-dimensional aromatic clusters which were 

widely used as weakly coordinating anions. (WCAs). [1-6] The weakly coordinating nature of these anions 

allows to stabilize the highly reactive fullerene cation, [C60] + , [7] and the first free silylium cation, 

[Mes3Si] + . [8] Their high resistance to oxidation is demonstrated by the successful preparation of salts 

containing strong oxidizers such as oxidized hexabromophenylcarbazole [7] and [NO] + . [9] 

In this contribution, we report the first systematic experimental and theoretical study on the oxidation and 

reduction of 1-carba-closo-dodecaborate anions. The gas-phase ionization enthalpies and the electron 

affinities for the parent [1-H-CB11H11] - , the undecahalogenated derivates [1-H-CB11X11] - (X = F, Cl, Br 

and I), the hexabrominated anions [1-H-CB11H5Br6] - and [1-H-CB11Me5Br6] - as well as for the Cmethylated, 

undecabrominated anion [1-Me-CB11Br11] - were assessed by quantum-chemical calculations. 

Therefore, full geometry optimizations of each anion along with the neutral and dianionic radicals were 

undertaken at the PBE0/def2-TZVPP level of theory. The electrochemical oxidation or reduction, 

respectively, of these anions in SO2 and CH3CN was investigated by square wave and cyclic voltammetry. 

Figure 4: CV (A) (ν = 0.2 V s −1 ) and SWV (B) of 

1.9 mM [nBu 4N][1-H-CB 11F 11] with 1.9 mM Fc in 

CH 3CN at 20±2 °C. 

Poster 45 

[1] I. Krossing, I. Raabe, Angew. Chem. Int. Ed. 2004, 43, 2066-2090; Angew. Chem. 2004, 116, 2116- 

2142; 

[2] S. H. Strauss, Chem. Rev. 1993, 93, 927-942; 

[3] K. Seppelt, Angew. Chem. Int. Ed. 1993, 32, 1025-1027; Angew. Chem. 1993, 105, 1074-1076; 

[4] S. Körbe, P. J. Schreiber, J. Michl, Chem. Rev. 2006, 106, 5208-5249 

[5] C. A. Reed, Acc. Chem. Res. 2010, 43, 121-128; 

[6] C. Knapp, Comprehensive Inorganic Chemistry II, 2012, Vol. 1, Chapter 1.25, in press. 

[7] C. A. Reed, K.-C. Kim, R. D. Bolskar, L. J. Mueller, Science, 2000, 289, 101-104; 

[8] K.-C. Kim, C. A. Reed, D. W. Elliott, L. J. Mueller, F. Tham, L. Lin, J. B. Lambert, Science, 2002, 

297, 825-827; 

[9] C. Bolli, C. Knapp, T. Köchner, Z. Allg. Anorg. Chem. 2012, 638, 559-564.

Poster 46 

Fig. 1. Part of the crystal structure of 

[Na(SO2)6]B12Br12[B12Br12] 

135 


The Oxidation of Perhalogenated Boron Clusters [B12X12] 2- (X = F, Cl, Br) 

Mathias Keßler and Carsten Knapp 

(mkessler@uni-wuppertal.de) 

Fachbereich C – Anorganische Chemie, Bergische Universität Wuppertal, Gaußstr. 20, 42119 

Wuppertal, Germany 

Deltahedral closo-borane dianions [BnHn] 2- feature a special binding situation which can be well 

understood by MO theory. [1] The perhalogenated closo-dodecaborates [B12X12] 2- (X = F, Cl, Br, I) stand 

out due to their exceptional stability resulting from their strong halogen-boron bonds. 

The oxidation of the closo-dodecaborates [B12R12] 2- (R = Me, alkoxy, aryloxy, hydroxy) and the structural 

characterization of the corresponding radical anions and the neutral hypercloso clusters could be 

accomplished up to now. [2-4] Oxidation of the perhalogenated closo-dodecaborates [B12X12] 2- (X = F, Cl, 

Br) is a challenging task due to the electron withdrawing effect of the halogens. However the replacement 

of conventional organic solvents by liquid sulfur dioxide and the usage of oxidation agents like arsenic 

pentafluoride allows the oxidation and the characterization of the radical [B12Cl12] ·- and neutral B12Cl12. [5] 

The oxidation of the perhalogenated closo-dodecaborates [B12X12] 2- (X = F, Cl, Br) and the 

characterization of the resulting radical anions [B12F12] ·- , [B12Cl12] ·- and [B12Br12] ·- and the hypercloso 

clusters B12Cl12 and B12Br12 will be presented. 

[1] M. A. Fox, K. Wade, Pure Appl. Chem. 2003, 1315. 

[2] T. Peymann, C. B. Knobler, M. F. Hawthorne, Chem. Commun. 1999, 2039. 

[3] a) T. Peymann, C. B. Knobler, S. I. Khan, M. F. Hawthorne, Angew. Chem. Int. Ed. 2001, 40, 1664 b) 

O. K. Farha, R. L. Julius, M. W. Lee, R. H. Huertas, C. B. Knobler, M. F. Hawthorne, J. Am. Chem. 

Soc. 2005, 127, 18243 c) M. W. Lee, O. K. Farha, M. F. Hawthorne, C. H. Hansch, Angew. Chem. 

Int. Ed. 2007, 46, 3018 

[4] N.-D. Van, I. Tiritiris, R. F. Winter, B. Sarkar, P. Singh, C. Duboc, A. Muñoz-Castro, R. Arratia- 

Pérez, W. Kaim, T. Schleid, Chem. Eur. J. 2010, 16, 11242. 

[5] R. T. Boeré, S. Kacprzak, M. Keßler, C. Knapp, R. Riebau, S. Riedel, T. L. Roemmele, M. Rühle, H. 

Scherer, S. Weber, Angew. Chem. Int. Ed. 2011, 50, 549.

Poster 47 

Heavy p-Block Analogues of Thiazyl Radicals 

136 


Thao T. P. Tran and Jeremy M. Rawson 

(tran1y@uwindsor.ca, jmrawson@uwindsor.ca) 

Department of Chemistry and Biochemistry, University of Windsor, 273-1 Essex Hall, 401 Sunset Avenue, 

Windsor, ON Canada N9B 3P4, Canada 

The physical properties of dithiazolyl radicals (A) have attracted considerable interest as magnetic and 

spin-switching devices [1] . We report here recent investigations into phosphorus-containing heterocycles 

with a view to generating the isoelectronic phosphorus radicals (B). Reaction of benzene or toluenedithiol 

with PCl3 using a modification of the literature method [2] affords the corresponding heterocycles C (R = 

H, Me). The reactivity of the chloride derivatives C is discussed including their reduction with elemental 

sodium to form the P-P σ-bonded dimer D and their Lewis acid character in reaction with AlCl3/GaCl3 to 

afford phosphenium-phosphine/arsine complexes F [3] . Oxidation of D with X2 (X = Br and I) occurs with 

P-P bond cleavage. 

[1] A. Alberola, J.M. Rawson and A.L. Whalley, J. Mater. Chem., 2006, 16, 2560. 

[2] M. Baudler, A. Moog, K. Glinka, U. Kelsch, Z. Naturforsch., Teil B, 1973, 28, 363. 

[3] N. Burford, P. J. Ragogna, J. Chem. Soc., Dalton Trans., 2002, 4307–4315.

Poster 48 

Brønsted Acids Containing Hexacoordinated Phosphorus Anions 

137 


Khatera Hazin, Paul W. Siu and Derek P. Gates 

(dgates@chem.ubc.ca) 



The development of solid, weighable Brønsted acids is of particular interest due to their potential use in 

bond activation reactions. [1] However, systems of the type H + [X] - are not generally isolable due to the 

inherent high reactivity of most anions with H + . The successful isolation of a Brønsted acid requires a 

weakly coordinating anion (WCA). For example, WCAs such as [B(C6F5)4] - and [Al{OC(CF3)3}4] - have 

successfully been employed to obtain isolable solid Brønsted acids. We have been interested in 

employing the known phosphorus (V) anion [1] - [2] as a charge balancing anion to afford isolable Brønsted 

acids. The synthesis and characterization of the solid, weighable HL2[1] (Figure 1, L = donor solvent) will 

be discussed in this presentation. [3] In addition, the reactivity and potential applications of HL2[1] will be 

surveyed. 

Figure 1: Hexacoordinated phosphorus (V) framework HL2[1]. 

[1] I. Krossing, I. Raabe, Angew. Chem. Int. Ed. Engl. 2004, 43, 2066-2090. 

[2] J. Lacour, C. Ginglinger, C. Grivet, G. Bernardinelli, Angew. Chem. Int. Ed. Engl. 1997, 36, 

608-610. 

[3] (a) P. W. Siu, D.P. Gates, Organometallics, 2009, 28, 4491-4499; (b) P.W. Siu, D.P. Gates, 

Can. J. Chem. 2012, In Press.

Poster 49 

Improved N-Heterocyclic Carbenes and Its Metal Complexes. 

138 


Jan Turek 1 , Illia Panov 2 , Zdeňka Padělková 1 and Aleš Růžička 1 

(jan.turek@upce.cz) 

1 Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of 


2 Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of 


N-heterocyclic carbenes (NHCs) have been known since the late 1960s when the pioneering work of 

Öfele and Wanzlick [1, 2] was published. But the real breakthrough in this field of chemistry came nearly 

thirty years later with the work ‘’A Stable Crystalline Carbene’’ published by Arduengo in 1991 [3] . NHCs 

have attracted worldwide attention not only because of their excellent bonding properties (coordination to 

various elements across the whole periodic system) but also because of their possible use as catalytically 

active ligands [4] comparable with cyclopentadienyls and phosphines. 

The main goals of the presented work were the synthesis of a set of new hybrid N-heteroleptic carbenes, 

among which one has an extra coordinating functional group, as well as their complexes with various 

metals. Afterwards, selected palladium complexes were tested for their possible catalytic activity. 

Fig. 1 Molecular structure of one of the studied compounds (Hydrogen atoms are omitted for clarity). 

The Science Foundation of Czech Republic is gratefully acknowledged for the financial support (Project 

no. P207/12/0223) 

[1] K. Öfele J. Organomet. Chem. 1968, 12, P42. 

[2] H. W. Wanzlick, H.-J. Schönherr Angew. Chem.Int. Ed. Engl. 1968, 7, 141. 

[3] A. J. Arduengo, R. L. Harlow, M. Kline J. Am. Chem. Soc. 1991, 113, 361. 

[4] D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606.

Poster 50 

139 


Theoretical Investigation of S2N2 Polymerization Employing Solid State 

Molecular Dynamics Simulations 

Teemu T. Takaluoma † , Kari Laasonen ‡ and Risto S. Laitinen † 

(teemu.takaluoma@oulu.fi) 

† Department of Chemistry, University of Oulu, P.O Box 3000, FIN-90014, University of Oulu, Finland 

‡ Department of Chemistry, Aalto University, P.O Box 16100, FIN-00076 Aalto, Finland 

(SN)x is a unique metallic polymer with superconducting properties at low temperatures (Tc < 0.3 K). [1,2] 

The classical synthetic route to produce the crystalline polymer goes through spontaneous topotactical 

polymerization of S2N2 ring molecules. [1,3,4] 

The topotactical polymerization reaction of crystalline S2N2 to (SN)x has been investigated with quantum 

mechanical solid state molecular dynamics simulations for the first time. Simulations have been 

performed using a simulation cell (17.94 Å, 15.07 Å, 16.99 Å) composing of 64 S2N2 molecules. 

The polymerization of S2N2 is a very slow reaction and usually takes hours to reach completion at RT. 

Such timescales are beyond conventional MD approaches, where the usual simulation time limits are 

measured in pico- or nanoseconds. Practical simulation timescales are achieved by compression of the 

crystalline ring material with high isotropic pressure of 50 GPa (and at 600 K). 

When the ring polymerization is initiated, the whole system undergoes a very rapid reaction to a fully 

polymerized crystalline material. Polymerization takes place in direction of the crystallographic a axis. 

The rings undergo single-bond cleavage and react along row of rings in ac-plane. Metastable side 

reactions are observed in the direction of b and c axes. Out-of-plane ring opening is also observed as a 

possible pathway. Towards the end of the reaction, the metastable species dissociate and in the final 

product only polymers in direction of a axis remain. 

Figure 1: Progress of polymerization at 0 %, 25 % and 100 % of completion. (revPBE/DZVP-MOLOPT- 

SR with CP2K) 

[1] Chivers, T.; Laitinen, R. S. In Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, 

Selenium and Tellurium; Devillanova, F. A., Ed.; Royal Society of Chemistry Publishing: Cambridge, 

U.K., 2007; p 223. 

[2] Greene, R. L.; Street, G. B.; Suter, L. J. Phys Rev. Lett. 1975, 34, 577. 

[3] Labes, M. M.; Love, P.; Nichols, L. F. Chem. Rev. 1979, 79, 1. 

[4] Cohen, M. J.; Garito, A. F.; Heeger, A. J.; MacDiarmid, A. G.; Mikulski, C. M.; Saran, M. S.; 

Kleppinger, J. J. Am. Chem. Soc. 1976, 98, 3844.

140 


Six Membered N,N-Diazastanna Cycles Based On Β-Diketiminate Complexes 

Roman Olejnik, Zdenka Padelkova and Ales Ruzicka 

(roman.olejnik@email.cz) 


Pardubice, Studentska 573, CZ-532 10, Pardubice, Czech Republic 

β-Diketiminates (BDI) play important role in organic and organometallic chemistry. Bifunctional BDI 

contain appropriate functional groups which can extra coordinate metal centre and it can affect higher 

stability of final metal complexes. These metal-containing species can be used in many areas of 

chemistry [1] . Divalent tin complexes were used for carbon dioxide activation [2] or as initiators for 

polymerization of rac-lactide [3] . Ligands can be prepared generally from 1,3-diones and primary aromatic 

amines [4] . We are interested in BDI ligand, which is prepared from acetylacetone and o-anisidine (L CO H) 

because of donor groups in convenient positions. This type of ligand forms six-membered diazametalla 

rings by transmetallation reaction of lithium complexes with metal chlorides (M = Sn, Ge, Bi) or direct 

synthesis from L CO H BDI and metal amides (M = Sn, Nd, La, Sm). Prepared heterocyclic tin(II) 

complexes were further tested especially in terms of reactivity with organic substrates. All prepared 

compounds were characterized by multinuclear NMR spectroscopy and when it was possible by XRD 

techniques. 

Si4 

N3 

Si3 

C1 C3 

N1 N2 

O1 

Poster 51 

C2 

Nd1 

Figure. The molecular structure of one of compounds studied. 

Authors would like to thank the Czech Science Foundation (grant no. 104/09/0829) for financial support. 

[1] M. H. Chisholm, J. C. Gallucci and K. Phomphrai; Inorg. Chem. 2005, 44, 8004. 

[2] L. Ferro, P. B. Hitchcock, M. P. Coles, H. Cox and J. R. Fulton; Inorg. Chem. 2011, 50, 1879. 

[3] A. P. Dove, V. C. Gibbon, E. L. Marshall, H. Rzepa, A. J. P. White, D. J. J. Williams; J. Am. Chem. 

Soc. 2006, 128, 9834. 

[4] R. Olejnik, Z. Padelkova, M. Horacek and A. Ruzicka; Main Group Met. Chem. 2012, 35, 13. 

O2 

N4 

Si2 

Si1

Poster 52 

141 


Structural Characterization of a [Pd3Cl9(μ3-Se6)] 3- Anion Containing the Se6ring 

A. Eironen, R. Oilunkaniemi and R. S. Laitinen 

(aino.eironen@oulu.fi) 

Department of Chemistry, P.O. Box 3000, FI-90014, University of Oulu, Finland 

We have recently reported the structures of two palladium complexes [PdCl2{Se,Se′-Se4(N t Bu)n}] (n = 3, 

4) containing novel cyclic selenium imides. [1] These two complexes were isolated from the 1:2 reaction of 

[PdCl2(NCPh)2] with Se(N t Bu)2 which was synthesized in situ by the reaction of SeCl4 with t BuNH2 in a 

molar ratio of 1:6. We have also studied the related complexation reaction of SeCl2 and t BuNH2 with 

[PdCl2(NCPh)2]. The reaction resulted in the formation of a new palladium complex, 

( t BuNH3)3[Pd3Cl9(μ3-Se6)], containing a neutral μ3-bridging cyclohexaselenium ligand coordinating to 

three PdCl3 fragments. There are only a few transition metal complexes containing the cyclohexaselenium 

ligand: [PdCl2(Se6)], [2] [PdBr2(Se6)], [2] [(AgI)2Se6)], [3] [Ag2(Se6)(SO2)2][Sb(OTeF5)6]2, [4] 

[Ag2(Se6)(SO2)4][Al(OC(CF3)3)4]2, [4] [Ag2(Se6)][AsF6]2, [4] [Ag(Se6)][Ag2(SbF6)3] [4] . 

[1] M. Risto, A. Eironen, E. Männistö, R. Oilunkaniemi, R. S. Laitinen, and T. Chivers, Dalton Trans., 

2009, 8473. 

[2] K. Neiniger, H. W. Rotter, and G. Thiele, Z. Anorg. Allg. Chem., 1996, 622, 1814. 

[3] H.-J. Deiseroth, M. Wagener, and E. Neumann, Eur. J. Inorg. Chem. 2004, 4755. 

[4] D. Aris, J. Beck, A. Decken, I. Dionne, J. Schmedt auf der Günne, W. Hoffbauer, T. Köchner, I. 

Krossing, J. Passmore, E. Rivard, F. Steden, and X. Wang, Dalton Trans., 2011, 40, 5865.

142 


N-Heterocyclic Carbene Borane-Containing π-Conjugated Systems 

Kazuhiko Nagura 

and Shigehiro Yamaguchi a 

, a Shohei Saito, a Roland Fröhlich, b Frank Glorius, b 

(yamaguchi@chem.nagoya-u.ac.jp) 

a 

Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya, 464- 

8602, Japan, b Organisch-Chemisches Institut, Westfälische Wilheims-Universität Münster, Corrensstrasse 

40, 48149 Münster, Germany 

N-Heterocyclic carbenes (NHCs) react with trivalent boranes 

to form Lewis base/acid complexes. Recently, the NHCborane 

chemistry has attracted increasing attention because of 

their intriguing reactivity as the catalysts and reactants. In this 

work, we focus our attention on the NHC-boranes from a 

materials point of view. We designed and synthesized 

thiophene-based π-conjugated systems 1–3 bearing NHCborane 

moieties at the terminal positions. [1] The 

intramolecular coordination of the NHC to the boryl group 

fixes the NHC-thiophene skeleton in a coplanar fashion, 

ensuring the effective π-conjugation with each other. In 

addition, the zwitterionic structure of the NHC-borane moiety endows the thiophene π skeleton with 

highly polar and electron-donating characters. 

In the absorption spectra, the thiophene derivative 1a shows negative solvatochromism from λmax 349 nm 

in cyclohexane to λmax 327 nm in DMSO, which demonstrates the large dipole moment in the ground 

state. Notably, upon irradiation of a UV light to 1a under a nitrogen atmosphere, a photoreaction 

smoothly took place to form a borabicyclo[4.1.0]heptadiene skeleton with a drastic color change from 

colorless to deep yellow (λmax 429 nm). In contrast, the expanded bithiophene derivatives 2 and 3 were 

inert to this photoreaction. The cyclic voltammograms of 2 and 3 show low oxidation potentials at E1/2 = 

+0.28 V and Epc = +0.27 V, respectively, which indicate the NHC-borane moiety is a powerful unit to 

make the π skeleton electron-donating. X-ray crystal analysis of 1a and 2 confirmed the coplanar 

geometry between the thiophene and the NHC rings. In addition, as a consequence of a completely planar 

conformation of the bithiophene moiety, 2 forms a slipped face-to-face π-stacking array, in which the 

electron-rich thiophene rings are overlapped with the electron-deficient benzimidazolidene moieties of the 

adjacent molecules with the interfacial distance of 3.51 Å. 

Figure 1. Absorption spectral change of 

1a in CH2Cl2 upon irradiation of a UV 

Poster 53 

Figure 2. Packing structure of 2. 

[1] K. Nagura, S. Saito, R. Fröhlich, F. Glorius, S. Yamaguchi, Angew. Chem. Int. Ed., in press.

Oxidative Addition of Aryl- and Alkylditellurides to Pt(0) Centres 

143 


M. M. Karjalainen 1 , T. Wiegand, 2 A. Wagner, 2 H. Görls, 2 R. Oilunkaniemi, 1 R. S. Laitinen, 1 W. Weigand 2 

(minna.karjalainen@oulu.fi) 

1 Department of Chemistry, University of Oulu, P. O. Box 3000, FI-90014 University of Oulu, Finland, 

2 Institut für Anorganische und Analytische Chemie, Humboldstrasse 8, 07743, Friedrich-Schiller- 

Universität, Jena, Germany 

Oxidative addition of aryl- and alkyldiselenides to zerovalent platinum and palladium centres occurs 

usually with the cleavage of chalcogen-chalcogen bond. In the corresponding reactions of ditellurides, the 

[1, 2] 

Te-C bond cleavage is also possible. 

In this contribution the oxidative addition of ditellurides R2Te2 to [Pt(nb)(PP)] (nb = norbornylene) using 

various ditellurides (R = phenyl, 2-thienyl, n-butyl, t-butyl) and chelating diphosphines (PP = 1,2bis(diphenylphosphino)ethane, 

1,2-bis(diphenylphosphino)benzene, 1,2-bis(diphenylphosphino) 

naphthalene, 1,2-bis(diphenylphosphino)propane). The reactions produce two types of tellurolato 

complexes [Pt(TeR)2(PP)](1) and [Pt(TeR)(R)(PP)](2). The product distribution was monitored by 

31 1 

P{ H} NMR spectroscopy and was found to depend strongly on the electron withdrawing or donating 

nature of the organic substituent of the ditelluride, as well as on the bite angle of diphosphine and the 

rigidity of diphosphine structure. In the reaction of (TePh)2 with [Pt(nb)(dppn)] the formation of 1 and 2 

depend on the molar ratio of the reactants with excess of ditelluride, 1 is formed and with that of 

[Pt(nb)(dppn)], 2 is the main product. 

1 

Poster 54 

[1] R. Oilunkaniemi, R. S. Laitinen, M. Ahlgrén, J. Organomet. Chem. 2001, 623, 168. 

[2] A. Wagner, L. Vigo, R. Oilunkaniemi, R. S. Laitinen, W. Weigand, Dalton Trans. 2008, 3535. 

2

Poster 55 

Single Source Precursors as a Route to Doped Graphites 

Timothy C. King and Dominic S. Wright 

(tk405@cam.ac.uk) 

Department of Chemistry, University of Cambridge, UK 

144 


Boron-doped graphite provides a range of technological differences compared to undoped graphite, 

including reduced oxidation and erosion rates (specifically with respect to plasma facing materials used in 

fusion reactors) and improved electrode performance in Li ion batteries. However, numerous previous 

invesigations have succeeded only with limited boron doping and normally samples are only several 

monolayers thick. Interest has recently been piqued in this area due to several computational studies on 

the hydrogen storage ability of boron-doped graphite, specifically BC3. These studies have stressed the 

importance of developing a reliable synthetic method of obtaining bulk samples of boron-rich material 

since chemisorption of H2 relies on cooperativity between the layers within the bulk and, for example, 

boron-doped monolayers and graphite itself are inactive in H-H bond cleavage. 

We describe here a single-source method of obtaining bulk amounts of ‘BC3’. This involves a facile 

carbonisation/graphitisation step that produces a material capable of storing 5 wt% hydrogen (only slight 

below the US-DoE minimum target). 

Figure 5. The synthesis of boron doped graphites from a single-source precursor. 

[1] J. Kouvetakis, R. Kaner, M. Sattler, and N. Bartlett, J. Chem. Soc., Chem., 1986, 1758-1759. 

[2] C. Lowell, J. Am. Ceram. Soc., 1967, 50, 142-144. 

[3] C. Zhang and A. Alavi, J. Chem. Phys., 2007, 127, 214704. 

[4] X. Sha, A. Cooper, and W. B. III, J. Phys. Chem., 2010, 3260-3264.

Poster 56 

145 


Planarized Triphenylboranes: Unique Structural Change in the Excited State 

Tomokatsu Kushida, 

a 

Department of Chemistry, Nagoya University, 

a Ayumi Shuto, a Tetsuro Katayama, b,d Syoji Ito, b Hiroshi Miyasaka, b Eri Sakuda, c 

Noboru Kitamura, c Cristoher Camacho Leandro, a Stephan Irle, a,e and Shigehiro Yamaguchi a,e 

(yamaguchi@chem.nagoya-u.ac.jp) 

kushida@chem.nagoya-u.ac.jp b Department of Chemistry 

and Center for Quantum Material Science under Extreme Conditions, Osaka University, c Department of 

Chemistry, Hokkaido University, d JST-PRESTO, e JST-CREST, Furo, Chikusa, Nagoya, 464-8602, Japan 

We have recently reported the synthesis of triphenylboranes planarized with three methylene tethers. [1] In 

the study of photophysical properties, we found that the compound exhibited dual emissions at room 

temperature, as shown in Figure 1. This phenomenon is unique for the planarized skeleton and not 

observed for normal unconstrained triarylboranes, such as trimesitylborane. To elucidate the origin of the 

luminescence properties, we have now measured the emission lifetimes as well as the transient absorption 

spectra, and rationalized those results based on the theoretical calculations in the excited state. 

The emission lifetimes were determined for each emission band. In the transient absorption spectra, two 

transient species corresponding to each lifetime of the two emission bands were successfully observed. 

Based on these experimental results as well as the structural optimization in the excited state, we 

concluded that this compound can have two local minimum structures, planar and bowl-shaped structures, 

in the lowest singlet excited state, each of which emits a fluorescence at the different wavelength (Figure 

2). Phosphorescence properties at a low temperature will also be described. 

[1] Z. Zhou, A. Wakamiya, T. Kushida, S. Yamaguchi J. Am. Chem. Soc., 2012, 134, 4529.

Poster 57 

146 


Easy Access to Backbone P-functionalized N-heterocyclic Carbenes and 

Complexes Thereof – en route to Novel Functional Ionic Liquids 

Paresh Kumar Majhi, Susanne Sauerbrey and Rainer Streubel 

( pmajhi@uni-bonn.de) 

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, 

Gerhard-Domagk-Str.1, 53121 Bonn, Germany 

Since the discovery of “bottleable” NHC’s by Arduengo et al., [1] carbene chemistry has received renewed 

attention in coordination and main group chemistry, homogenous catalysis, and beyond. In recent years, 

introduction of an additional donor atom into an NHC has been subject of increased attention. In this 

regard, we will present the synthesis of mono- and di-phosphanyl and phosphoryl (n = 1, 2) (and/or P V ; E 

= O, S, Se) substituted imidazol-2-thiones [2] (1, 4) and imidazolium salts (2, 5), obtained via oxidative 

desul-furization [3] of 1 and 4, respectively. Furthermore, reactions of 2 allow for in situ com-plexation to 

yield 3 (Scheme); evidence for P-functional NHC’s 6 will be also provided. [4] 

[1] Arduengo III, A. J.; Harlow, R.L.; Kline, M. J. Am. Chem. Soc.1991, 113, 361-363. 

[2] Sauerbrey, S.; Majhi, P.K.; Schnakenburg, G.; Arduengo III, A. J.; Streubel, R. Dalton Trans. 2012, 

41, 5368-5376 and Heteroatom Chem. 2012, accepted. 

[3] Morel, G. Synlett. 2003, 14, 2167-2170. 

[4] Majhi, P.K.; Schnakenburg, G.; Arduengo III, A. J.; Streubel, R. to be published.

Poster 58 

Theoretical Study on SET-mediated Selective Bond Activation in 

Oxaphosphirane Complexes 

147 


Arturo Espinosa a and Rainer Streubel b 

(artuesp@um.es) 

a Depto. Química Orgánica, Universidad de Murcia, Spain 

b Institut für Anorganische Chemie, Rheinischen Friedrich-Wilhelms-Universität Bonn, Germany 

Despite their potential use as powerful building blocks in organic synthesis, there is still scarce 

knowledge about heterocycles possessing three differently polar ring bonds such as in oxaphosphirane [1] 

and azaphosphiridines, [2] featuring a three-coordinated phosphorus centre. The chemistry of 

oxaphosphirane [3] (as well as azaphosphiridine [4] ) complexes 1 is now emer-ging in ligand-centered ring 

forming reactions, as ring enlargement [5] and opening [6] reactions, taking advantage of the pentacarbonylmetal(0) 

moieties as "inorganic protecting groups". Full exploration of oxaphosphirane chemistry would 

require the development of highly selective methods for exocyclic P-M and P-R bond cleavage while 

retaining the ring structure. 

In this work, we provide first-time 

insights into the intrinsic strength of 

exocyclic bonds of phosphorus in 

oxaphosphirane complexes 1, 

following the me-thodology used in 

the case of azaphosphiridine 

analogues. [7] The heterolytic cleavage 

in 1 leading to a carbocation R + and a 

oxaphosphiranide complex 2 - 

constitutes the lowest energy process of exocyclic P-R bond dissociation, especially if the group R is 

bulky and able to efficiently stabilize the positive charge, i.e. triphenylmethyl (trityl). The energies 

required for a P-M bond cleavage are about 30 kcal mol -1 and decrease with increasing bulk of the R 

substituent and on going from Cr to Mo. The reactivity of complexes 1 towards SET reactions was 

analysed using the facile VBSD (Variation on Bond Strength Descriptors) methodology, thus enabling the 

design of synthetically useful strategies addressing decomplexation and P-functionalization: reductive 

SET reactions (sodium naphthalenide) enable selective P-M bond cleavage (= decomplexation) for the 

case of P-Me and P- t Bu substitution, whereas reductive P-R bond cleavage is favored in the case of the Ptrityl 

complexes and results in the formation of the (anionic) oxaphosphiranide complex 2 - which may be 

regarded as a potential key intermediate for further P-functionalization. 

[1] For σ 3 λ 3 -oxaphosphiranes proposed as reactive intermediates: Bartlett, P. A.; Carruthers, N. I.; 

Winter, B. M. and Long, K. P. J. Org. Chem. 47 (1982) 1284. 

[2] For 1,2λ 3 -azaphosphiridines, see: a) Niecke, E.; Seyer, A. and Wildbredt, D.-A. Angew. Chem. 96 

(1981) 687. b) Dufour, N.; Camminade, A.-M. and Majoral, J.-P. Tetrahedron Lett. 30 (1989) 4813. 

[3] a) Bauer, S.; Marinetti, A.; Ricard, L. and Mathey, F. Angew. Chem. Int. Ed. Engl. 29 (1990) 1166; b) 

Streubel, R.; Kusenberg, A.; Jeske, J. and Jones, P.G. Angew. Chem. Int. Ed. Engl. 33 (1994) 2427. 

[4] a) Streubel, R.; Ostrowski, A.; Wilkens, H.; Ruthe, F.; Jeske, J. and Jones, P. G. Angew. Chem. Int. 

Ed. Engl. 36 (1997), 378; Vlaar, M. J. M.; Valkier, P.; de Kanter, F. J. J.; Schakel, M.; Ehlers, A. W.; 

Spek, A. L.; Lutz, M. and Lammertsma, K. Chem. Eur. J. 7 (2001) 3552. 

[5] a) Helten, H.; Marinas Pérez, J.; Daniels, J. and Streubel R. Organometallics 28 (2009) 1221; b) 

Pérez, J. M.; Helten, H.; Schnakenburg, G. and Streubel, R. Chem. Asian J. 6 (2011) 1539. 

[6] a) Pérez, J. M.; Helten, H.; Donnadieu, B.; Reed, C. and Streubel, R. Angew. Chem. Int. Ed. 49 (2010) 

2615; b) Pérez, J. M.; Albrecht, C.; Helten, H.; Schnakenburg, G. and Streubel, R. Chem. Commun. 46 

(2010) 7244. 

[7] a) Espinosa, A.; Gómez, C. and Streubel, R. Inorg. Chem. (2012) DOI: 10.1021/ic300522g.

Poster 59 

148 


Synthesis and Characterization of Novel Cyclic Organotin Compounds 

J. Binder, B. Seibt, R. Fischer and F. Uhlig 

(binder@tugraz.at) 

Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austria 

A large number of reports concerning derivatives with silicon and carbon groups 

(-R2Si-CH2-)n in the ring skeleton has been published in literature. However, only few studies are focused 

on the synthesis and reaction behavior of similar compounds containing also the higher elements of group 

14. 

For that purpose different “flexible" spacers of type α-ω-bis(chlorodimethylsilyl)alkane (alkane chain 

length n = 2, 3, 4) [1] are used with diphenyltindichloride in the presence of magnesium in a Wurtz-type 

reaction yielding derivatives with various ring sizes. Also "rigid" spacers of type α-ωbis(chlorodimethylsilyl)xylene/benzene 

are used in a similar reaction resulting in a series of siliconbridged 

tin-indane derivatives. Furthermore the formation of analogous tin-indane derivatives with carbon 

as bridging atoms is reported. 

The preparation of these carbon bridged tin-indane derivatives using Wurtz-type coupling reactions 

does not lead to the selective formation of tin-indane derivates. Tetraline derivatives are formed as major 

byproduct. Therefore, we report here also on a novel reaction pathway towards the selective formation of 

tin-indane derivates (Scheme 1). 

Scheme 1: Formation of carbon bridged tin-indane derivatives 

[1] Binder, J., Diplomarbeit, TU Graz, 2008 

[2] Zarl, E., Ph. D. Dissertation, TU Graz, 2008 

[3] Zarl, E., Uhlig, F., Zeitschrift für Naturforschung / B 64b, 2009, 1591 - 1596 

[2, 3]

Poster 60 

Phosphorus-Based Flame Retardants for Paper 

149 


Andrew M. Priegert, 1 Paul W. Siu, 1 Thomas Q. Hu 2 and Derek P. Gates 1 

(aprieger@chem.ubc.ca, dgates@chem.ubc.ca, thomas.hu@fpinnovations.ca) 

1 Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British 

Columbia, V6T 1Z1, Canada 

2 FPInnovations – Pulp and Paper Division, 3800 Wesbrook Mall, Vancouver, British Columbia, V6S 

2L9, Canada 

Traditional halogenated flame retardants such as polybrominated diphenyl ethers (PBDEs) are either 

being phased out or have already been banned in many jurisdictions worldwide. To replace them, there is 

a growing need for non-halogenated and non-leachable alternatives. As part of the growing interest in 

phosphorus-based flame retardants, novel phosphorus-containing polymers have been synthesized from 

the phosphaalkene MesP=CPh2 (Mes = 2,4,6-trimethylphenyl, Ph = C6H5). Discussed herein are the 

results of tests to evaluate their flame retardant properties when used to treat paper. The TAPPI 

(Technical Association of Pulp and Paper Industry) Standard Method T461 cm-00 was followed using 

paper made from thermomechanical pulp coated with polymer. Also to be presented are the results of 

thermogravimetric analyses (TGA) carried out on treated paper samples to evaluate thermal stability. 

[1] Yam, M.; Chong, J. H.; Tsang, C.-W.; Patrick, B. O.; Lam, A. E.; Gates, D. P. Inorg. Chem. 2006, 

45, 5225-5234 

[2] Noonan, K. J. T.; Gates, D. P. Angew. Chem. Int. Ed. 2006, 45, 7271-7274 

[3] Bates, J. I.; Dugal-Tessier, J.; Gates, D. P. Dalton Trans, 2010, 39, 3151-3159

Poster 61 

Zeolite Inclusion Compounds of 1,2,3,5-Dithiadiazolyl Radicals 

150 


Hugh J. Cowley, Douglas R. Pratt and Jeremy M. Rawson 

(cowleyh@uwindsor.ca, jmrawson@uwindsor.ca) 

Department of Chemistry and Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON 

N9B 3P4, Canada 

A range of 1,2,3,5-dithiazolyl radicals such as 1 were synthesised and included within a faujasite (zeolite 

Y) lattice. Thermal gravimetric analysis and differential scanning calorimetry were used to determine 

radical loading within the lattice as well as the enthalpy of inclusion. The materials were characterised by 

powder X-ray diffraction and their magnetic character was determined by EPR spectroscopy. The effect 

of inclusion upon radical dimerisation and stabilisation will be discussed.

Poster 62 

Synthesis and Characterization of 1,3,2-Diathiazolyl Radicals 

151 


Justin D. Wrixon, John J. Hayward and Jeremy M. Rawson 

(wrixon@uwindsor.ca, jmrawson@uwindsor.ca) 

Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON, N9B 

3P4, Canada 

A cost-efficient synthetic route to dialkoxy-benzene-substituted 1,3,2-dithiazolyl radicals has recently 

been developed by the Rawson group. [1] This methodology has been extended to a series of dialkoxysubstituted 

1,3,2-benzodithiazolyl radicals, including dioxyl-benzo-1,3,2-dithiazolyl (DOXBDTA) and 

dioxepinyl-benzo-1,3,2-dithiazolyl (DOXEBDTA). The characterisation of these systems and the 

application of this methodology to more complex systems will be discussed. 

[1] Alberola, A., Eisler, D., Less, R.J., Navarro-Moratalla, E., Rawson, J.M., Chem. Comm. 2010, 46, 

6114-6116.

152 


Structure and Reactivity of Low Oxidation State Indium Compounds with 

“Non-Innocent” Ligands 

Christopher J. Allan, Benjamin F. T. Cooper, Hugh J. Cowley, Jeremy M. Rawson, Charles L. B. 

Macdonald 

(allanc@uwindsor.ca, cmacd@uwindsor.ca) 

University of Windsor, Canada 

In addition to exhibiting interesting fundamental chemistry, low oxidation state indium(I) compounds 

have proven to be effective catalysts in a variety of organic transformations (e.g. allylations at carbonyls, 

imines, benzylic ethers). [1] However, the coordination of neutral ligands, which may tune the selectivity or 

activity of such catalysts, to low-oxidation state indium halides generally results in disproportionation, 

producing indium metal and higher oxidative species. [2-4] In contrast, we report that the reaction of InOTf 

(OTf = trifluoromethanesulfonate) 5 with “non-innocent” α-diimine (DAB) ligands afforded coloured 

products with no signs of indium metal being generated. We find that substituents present on the ligand 

can play a large role in the electronics of the system and in some instances yields radical and/or polymeric 

materials. In this work we present computational investigations, EPR spectra, cyclic voltammetry and Xray 

crystal structures in order to elucidate the structure and chemistry of these InDAB complexes. 

Ar 

OTf 

In 

N N 

Ar 

R=Me 

Ar=Mes or Dipp 

Ar 

Poster 63 

InOTf 

+ 

N N 

R R 

Ar 

R=H 

Ar=Mes 

[1] Schneider, W.; Kobayashi, S. Acc. Chem. Res. 2012 ASAP 

[2] Pardoe, J. A. J.; Downs, A. J. Chem Rev. 2007, 107, 2. 

[3] Green, S.; Jones, C.; Stasch, A. Angew, Chem. Int. Ed. 2007, 46, 8618 

[4] Cole, M. L.; Jones, C.; Kloth, M. Inorg. Chem. 2005, 44, 4909. 

[5] Cooper, B. F. T.; Macdonald, C. L. B. New J. Chem. 2010, 34, 1551. 

N 

N 

Mes 

In 

Mes 

OTf 

TfO 

Mes 

In 

N 

N 

Mes n

Poster 64 

EED studies on Chromium borylene 

H. Braunschweig † , Ch. Lehmann ‡ , K. Radacki 

(K.Radacki@uni-wuerzburg.de) 

† 

Universität Würzburg, Am Hubland, 97074 Würzburg 

‡ 

Max-Planck-Institut für Kohlenforschung; Mülheim an der Ruhr, Germany 

153 

† 


Transition metal complexes of boron with electron-precise (2c,2e) M−B bonds have become an area of 

widespread interest in the past decade. Terminal and dinuclear borylene complexes LxM=BR, 

LxM−B(R)−M’Lx in particular owe much of their importance to the fact that they are closely related to 

pivotal organometallics such as carbonyl or vinylidene complexes. The structure of [(CO)5Cr=B=NR2] (1) 

was characterized by conventional single crystal diffraction already in 2001, [1] and analyzed in detailed by 

means of theoretical chemistry in 2007. [2] The investigation of the electronic structure on the basis of 

experimental electron densities (EED) in [{Cp(CO)2Mn}2(µ-BtBu)] (2), comprising bridging borylene 

ligand, showed unexpected features in Laplacian distribution of the central Mn2B-ring. [3] Recently, we 

were able to perform a high resolution X-Ray experiment on 1 and subsequent refinement in multipole 

formalism of Hansen and Coppens. [4] That gave us opportunity to analyze both theoretical and 

experimental data of 1, as well as to compare experimental densities of terminal borylene 1 with these of 

bridging borylen 2. 

Experimental molecular graph (left) and Distribution of ∇ 2 ρ (right) of 1. 

[1] H. Braunschweig, M. Colling, C. Kollann, H.G. Stammler, B. Neumann Angew. Chem. Int. Ed. 2001, 

40, 2298−2300. 

[2] B. Blank, H. Braunschweig, M. Colling-Hendelkens, C. Kollann, K. Radacki, D. Rais, K. Uttinger, 

G. Whittell Chem. Eur. J. 2007, 13, 4770−4781. 

[3] U. Flierler et al. Angew. Chem. Int. Ed. 2008, 47, 4321−4325. 

[4] N.K. Hansen, P. Coppens Acta Cryst. 1978, A34, 909−921. 

Acknowledgment: This work was supported by the Deutsche Forschungsgemeinschaft within SPP1178.

Poster 65 

Phosphorus-Containing Copolymers for Suzuki Cross-Coupling 

154 


Tom H. H. Hsieh, Thomas W. Hey and Derek P. Gates 

(thsieh@chem.ubc.ca) 



Traditionally, monodentate and bidentate phosphines have comprised the majority of phosphoruscontaining 

ligands in catalysis. The use of hybrid inorganic/organic phosphorus-containing polymers have 

been largely unexplored. We have previously reported that copolymers formed from the addition 

polymerization of phosphaalkene and styrene are capable of supporting transition metal cross-coupling 

catalysis. [1] We now report the recent developments in the ease of purification, increased substrate and 

catalyst scope, and ability to recycle the poly(methylenephosphine)-polystyrene copolymer (PMP-PS). 

Furthermore, copolymer microstructure and modifications, such as crosslinking with divinylbenzene, will 

be presented. 

[1] Tsang, C.-W.; Baharloo, B.; Riendl, D.; Yam, M.; Gates, D.P. Angew. Chem. Int. Ed. 2004, 43, 5682.

Poster 66 

Tin Catecholates 

155 


Zdenka Padelkova, Jan Turek, Hana Vankatova, Tomas Chlupaty and Ales Ruzicka 

(Zdenka.Padelkova@upce.cz) 



The chemistry of organotin(IV) diols (making five- or six-membered α, ω-dioxastanna cycles) was 

extensively studied in the past in order to investigate the influence of mainly glycolic or catecholic 

arrangement to the geometrical as well as optical properties of the tin central atom. In these days, tin 

catecholates are thoroughly investigated in many fields of applications, mainly for their possible use in 

catalysis. They can be used for example in radical polymerization processes [1] because of their unique 

ability of accepting various radicals, including carbon ones. This was proved by polymerization of styrene 

and methylmetacrylate in presence of bis(catecholate)tin(IV) complex. In addition these complexes play 

an important role in regulation of chain length and they also provide linear growth of molecular weight of 

product with growing conversion rates of reaction. The preparation, structure and reactivity of different 

tin and germanium catecholates have been studied by Barrau, Jurkschat and others. [2] 

Our current interest is focused on the reaction products of different C,N- and N,N-chelated tin(II and IV) 

complexes (Fig. 1) with quinones or catecholates. 

Fig. 1 Fragments of compounds studied 

The authors would like to thank the Grant Agency of the Czech Republic (grant no. P207/10/P092) for 

the financial support. 

[1] For example: L. B. Vaganova, E. V. Kolyakina, A. V. Lado, A. V. Piskunov, D. F. Grishin, Polymer 

Science, Ser. B, 2009, 51, 96. 

[2] For example: K. Jurkschat, N. Pieper, S. Seemeyer, M. Schuermann M. Biesemans, I. Verbruggen, R. 

Willem Organometallics 2001, 20, 868; J. Barrau, G. Rima, T. El-Amraoui, J. Organomet. Chem. 1998, 

561, 167.

Poster 67 

Cp big Complexes of Low Valent Main Group Metals 

Dominik Naglav and Andreas Schnepf 

(dominik.naglav@stud.uni-due.de, andreas.schnepf@uni-due.de) 

Fakultät für Chemie, Universität Duisburg-Essen, 45141 Essen, Germany 

156 


The reaction of KCp big [Cp big = C5(CH2C6H4- i Pr)5, C5(C6H5)5] with low valent main group metal sources 

like “Ga (+1) I” and Ge (+1) Cl under mild conditions yielded in the formation of novel cp big complexes. 

Depending on the low valent metal precursor the increased sterical demand of the ligand can not only 

avoid the formation of oligomeric species (in case of “GaI”) but can also enforce the formation of large 

cluster compounds (in case of GeCl). [1-3] 

We were able to synthesize a dynamic sandwich complex of germanium in the oxidation state +2 as a 

product of the controlled disproportionation reaction of Ge (+1) Cl with KCp big to Ge(Cp big )2 and metalloid 

cluster compounds (GenLm with n > m) and KCl. The solid state structure of (1) shows that in the case of 

the Cp iPr Bz5 ligand the formation of a bent conformation is preferred in solid state due to the lone-pair-π 

interaction of the carbenoid Ge 2+ metal center with two of the aromatic benzyl substituents of the cp. 

Theoretical investigations confirm that the parallel conformation is preferred by 3.4 kJ/mol in comparison 

to the bent conformation, which indicates that the parallel structure is mainly present in solution. 

Cryogenic 1 H-NMR studies verify this assumption as all benzyl substituents are equivalent in solution 

even at −80 °C . [1] 

Molecular structure of GeCp big 2 [Cp big = C5(CH2C6H4- i Pr)5] and equilibrium of the open and closed form 

of 1 in solution (theoretical calculations) 

[1] Dominik Naglav, Briac Tobey, Sjoerd Harder and Andreas Schnepf, submitted to ZAAC. 

[2] Andreas Schnepf, New. J. Chem., 2079-2092, 34, 2010. 

[3] Hansgeorg Schnöckel, Andreas Schnepf, Angew. Chem., 3682-3703, 114, 2002.

Poster 68 

(Me3Si)2NPCl2 – A Molecule with a “Disguised” PN-Moiety 

157 


Christian Hering, a Axel Schulz a,b and Alexander Villinger a 

(christian.hering@uni-rostock.de) 

a Universität Rostock, Institut für Chemie, Abteilung Anorganische Chemie, Albert-Einstein-Straße 3a, 

18059 Rostock, Germany; b Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein- 

Str. 29a, 18059 Rostock, Germany 

Molecules such as R(Me3Si)N-PCl2 (R = Ter, Mes*, SiMe3) that can release in situ a highly reactive 

dipolarophile [R-NP] + by Me3SiCl elimination in the presence of a Lewis acid (GaCl3), are often referred 

to as “disguised” dipolarophiles. These silylated dichlorophosphanes are excellent starting materials for 

the formation of tetrazaphospholes of the type, RN4P·GaCl3. Just recently we reported on the synthesis of 

an ionic liquid containing the [Me3Si-NP] + cation, which is formed, when (Me3Si)2NPCl2 (1) was reacted 

with GaCl3. [1] Following our interest in compounds with a binary N–Pn (Pn = P, As, Sb, Bi) moiety we 

have studied if elimination of a second equivalent Me3SiCl starting from 1 is possible. Therefore the 

application of 1 as a precursor for diatomic PN, the heavier homologue of N2, is envisioned. Analogous P2 

is well known and starting from a solution of P4 in hexane the transient species could be trapped with 

suitable organic acceptors. [2] 

In a first series of experiments the thermal release of Me3SiCl in 1 in the presence of the trapping reagent 

2,3-dimethyl-butadiene (dmb) was investigated resulting, according to 31 P NMR studies, in the clean 

conversion to a cyclotetraphosphazane [PN(dmb)]4 (2), [3] incorporating four PN-fragments. Substituting 

the chlorine atoms in 1 by triflate groups yields (Me3Si)2NP(OTf)2 which should also generate “PN” upon 

thermal elimination of TfOSiMe3. If this elimination is carried out in the presence of dmb, the formation 

of the spirocyclic compound [(Me3Si)NP(dmb)2][O3SCF3] (3) is observed. We present here first results on 

the application of 1 as a synthetic equivalent for PN in inorganic as well as in organic chemistry and 

report on the synthesis of new cyclic phosphazenes and their application as ligand in transition metal 

chemistry (Figure 1). 

Figure 1. Cyclotetraphosphazene 2 (left) and 2·W2(CO)7 (right). 

[1] (a) A. Villinger, P. Mayer and A. Schulz, Chem. Commun., 2006, 1236; (b) C. Hering, A. Schulz, A. 

Villinger, Angew. Chem. Int. Ed. 2012, 51, 6241-6245. 

[2] (a) N. A.Piro, J. S. Figueroa, J. T.McKellar, C. C. Cummins, Science 2006, 313, 1276. (b) D. Tofan, 

C. C. Cummins, Ang. Chem. Intl. Ed. 2010, 49, 7516. 

[3] K. D. Gallicano, N. L. Paddock, Can. J. Chem.1985, 63, 314.

Poster 69 

158 


Coordination Chemistry of the Pentacyanocyclopentadienide Anion 

Thomas C. Wilson, Robert J. Less and Dominic S. Wright 

(tcw35@cam.ac.uk) 

University of Cambridge, UK 

The pentacyanocyclopentadienide anion, 1 (Fig. 1), has been little studied and has been claimed to be 

‘almost totally non-coordinating’. [1] However, recent studies [2] have shown this not to be the case, and 

altering the synthesis to give a thermodynamic driving force for the reaction has proved successful (Eqn. 

1). 

The readily accessible sodium salt Na[1] can then be reacted with metal halide salts (Eqn. 2) to yield 

novel complexes. Due to the presence of five electron-withdrawing groups, 1 acts as a σ-donor through 

the cyano groups, rather than as a π ligand via the C5 ring. Both CoCl2 and CuCl2 were reacted with 

Na[1], and the resulting complexes are reported here. In addition to this, a family of Group 11 phosphine 

complexes involving 1 are also reported. [3] The latter are the first complete series of cyclopentadienyl 

compounds to be structurally characterised for any group in the Periodic Table. The ion paired gold 

complex, Au(PPh3)2[1], is shown below (Fig. 2). 

Figure 1 (left): The pentacyanocyclopentadienide anion, 1 Figure 2 (right): Au(PPh3)2[1] 

[1] A. F. Williams etal., Chem. Eur. J., 2009, 15, 5012 

[2] D. S. Wright etal., Chem. Eur. J., 2010, 16, 13723 

[3] D. S. Wright et al., Chem. Commun., 2011, 47, 10007

Poster 70 

159 


Supramolecular Chemistry of N-Alkyl-Benzo-2,1,3-Selenadiazolium Cations 

Lucia Myongwon Lee, Victoria B. Corless, Michael Tran, Dora P. Hsieh, Faisal Adampani, Christine Li 

and Ignacio Vargas-Baca (leem35@univmail.cis.mcmaster.ca, vargas@chemistry.mcmaster.ca) 

Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, 

Hamilton, Ontario, L8S4M1, Canada 

In supramolecular chemistry, there is increasing interest in the use of main-group secondary bonding 

interactions (SBIs) as a tool to control the structures and properties of materials. The efficient application 

of SBIs would require the use of the best supramolecular synthons, the structural motifs created by 

operations of supramolecular synthesis. The ideal supramolecular synthon would be strong and 

directional such features are characteristic of systems assembled by more than one contact point, for 

example, the [E-N]2 supramolecular synthon which is frequently formed by molecules containing the 

1,2,5-chalcogenadiazole ring in their structure. [1] Derivatives of 1,2,5-telluradiazole were shown to exhibit 

functional properties such as chromotropism and second-order non-linear optical activity. However, they 

are easily degraded by hydrolysis, which limits their application. [2] The selenium analogues behave in a 

similar fashion but with weaker intermolecular forces. The N-alkylated heterocycles display shorter SBI 

distances than their neutral analogues. [3,4,5] This observation suggests that the positive charge of the 

molecule enhances the electron acceptor ability of the chalcogen, strengthening the supramolecular 

interaction. Direct alkylation of benzo-2,1,3-selenadiazole had been regarded as difficult, being successful 

only with vigorous alkylating agents. [3,4,5,6] It was shown recently that in some cases the reaction with 

alkyl iodides does proceed in mild conditions, as long as it is carried out under an inert atmosphere. A 

more convenient method of preparation of the N-alkylated cations starts with the N-alkyl-ophenylenediamine 

and selenium dioxide in acidic medium. [7,8] This method enables the preparation of a 

wide range of derivatives that can be used as supramolecular building blocks, most notable are novel 

bridged dicationic species, capable of assembling extended structures. 

[1] (a) Cozzolino, A. F.; Vargas Baca, I.; Mansour, S.; Mahmoudkhani, A. H. J. Am. Chem. Soc. 2005, 

127, 3184; (b) Cozzolino, A. F.; Elder, P. J. W.; Vargas Baca, I. Coord. Chem. Rev. 2011, 255, 

1426. 

[2] (a) Cozzolino, A.F.; Whitfield, P. S.; Vargas-Baca, I. J. Am. Chem. Soc. 2010, 10, 4459; (b) 

Cozzolino, A. F.; Yang, Q.; Vargas-Baca, I. Cryst. Growth Des. 2010, 10, 4459. 

[3] Risto, M.; Reed, R. W.; Robertson, C. M.; Oilunkaniemi, R.; Laitinen, R. S.; Oakley, R. T. Chem. 

Commun. 2008, 3278. 

[4] Dutton, J. L.; Tindale, J. J.; Jenings, M. C.; Ragogna, P. J. Chem. Commun. 2006, 2474. 

[5] Berionni, G.; Pégot, B.; Marrot, J. CrystEngComm. 2009, 11, 986. 

[6] (a) Nunn, A. J.; Ralph, J. T. J. Chem. Soc. 1965, 6769; (b) Nunn, A. J.; Ralph, J. T. ibid. C 1966, 

1568. 

[7] (a) Eremeeva, G. I.; Strelets, B. K.; Efros, L. S. Khim. Geterotsikl. Soedin. 1975, 276; (b) Eremeeva, 

G. I.; Strelets, B. K.; Efros, L. S. Ibid. 1976, 340; (c) Eremeeva, G. I.; Akulin, Y. I.; Timofeeva, T. 

N.; Strelets, B. K.; Efros, L. S. ibid. 1982, 1129; (d) V.B. Corless, Senior Undergraduate Thesis, 

McMaster University 2012. 

[8] Neve, J.; Hanocq, M. Talanta 1979, 26, 15.

Poster 71 

Small Molecule Activation by Anti-Aromatic Boroles 

160 


Adrian Y. Houghton a , Cheng Fan a , Heikki M. Tuononen b and Warren E. Piers a 

(ayhought@ucalgary.ca) 

a Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 

1N4, Canada 

b Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland 

The past few years have witnessed an increasing interest in the five-membered unsaturated boracycles 

known as boroles. [1] These compounds are anti-aromatic, have high Lewis acidity, and possess interesting 

electronic properties. Recently, the Piers group has demonstrated the unexpected activation of 

dihydrogen by pentaarylboroles (figure 1). [2,3] This unique reactivity has prompted the investigation of the 

its mechanism, as well as the extension of the known borole library to include 1-boraindenes (figure 2). 

This presentation focuses on the kinetics of dihydrogen activation and the synthesis 1-boraindenes 

starting from diarylzirconocenes and diarylacetylenes. 

[1] Braunschweig, H.; Kupfer, T., Chem. Commun. 2011, 47, 10903–10914 

[2] A. Fan, C.; Mercier, L. G.; Piers, W. E.; Tuononen, H. M.; Parvez, M., J. Am. Chem. Soc, 2010, 132 

(28), 9604-9606. 

[3] Fan, C.; Piers, W. E.; Parvez, M., Angew. Chem. Int. Ed, 2009, 48 (16), 2955-2958.

Poster 72 

161 


Probing the Group Tolerance of a Li/Cl Phosphinidenoid Complex Using α-, 

β- and ω-Substituted Aldehydes 

Melina Klein and Rainer Streubel 

( melinaklein@uni-bonn.de) 

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard-Domagk- 

Str.1, 53121 Bonn, Germany 

First synthesis of a σ 4 λ 5 -oxaphosphirane [1] was reported by Röschenthaler (1978) and the first 

oxaphosphirane complexes were described by Mathey (1990) [2] but no further studies appeared. Although 

a new synthetic method was reported in the following years (1994-1997), namely the phosphinidene 

complex transfer reaction, [3] the breakthrough was achieved recently when Li/Cl phosphinidenoid 

complexes were reacted with aldehydes (2007). [4] Here, reactions of Li/Cl phosphinidenoid complex 2a, 

generated at low temperature, [4] with various aldehydes bearing a functional group in α-, β- or ω-position 

and/or ketones [5] to give oxa-phosphirane complexes 3-9 or an isomeric product (10) will be presented. In 

addition, first studies on reactions of complexes 2a,b with DMF will be reported. 

Interestingly, exclusively 1,2-cycloaddition [6] occurred thus showing clear preference of the nucleophilic 

intermediate 2. NMR data, structures as well as the case of atropisomerism at the exo P-C bond in 

complexes 5-9 will be discussed. [6] Furthermore, preliminary results on reductive SET ring-opening 

reactions of some oxaphosphirane complexes using the systems Ti(Cp)2Cl2/Zn, TiCpCl3/Zn and 

TiCl3(thf)3 will be presented. 

[1] Röschenthaler, G.V.; Sauerbrey, K.; Schmutzler, R. Chem. Ber. 1978, 111, 3105. 

[2] Bauer S.; Marinetti, A.; Ricard, L.; Mathey, F. Angew. Chem. 1990, 102, 1188. 

[3] Streubel, R.; Kusenberg, A.; Jeske, J.; Jones, P. G. Angew. Chem. 1994, 106, 2564. 

[4] Özbolat, A.; von Frantzius, G.; Nieger, M.; Streubel, R. Angew. Chem. 2007, 119, 9488. 

[5] Pérez, J.M.; Klein, M.; Kyri, A.; Schnakenburg, G.; Streubel, R. Organometallics 2011, 30, 5636. 

[6] Streubel, R., Klein, M.; Schnakenburg, G. Organometallics 2012, DOI: 10.1021/om300177c.

Poster 73 

162 


Structural Diversity and Reactivity of New Phosphine-Stabilized Antimony 

Centers 

Saurabh S. Chitnis and Neil Burford 

(sschitnis@gmail.com) 

Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada 

Coordination chemistry has been applied successfully to achieve a variety of rare and reactive bonds 

between the heavy pnictogen elements (P, As, Sb, and Bi). [1-3] We have reported on the structural diversity 

observed in bidentate phosphine complexes of antimony-centered cations, [4] and have since discovered 

additional P-Sb bonding frameworks, highlighting a rich structural chemistry of ligand-stabilized 

antimony centers. Considering the metallic nature of antimony and its ability to achieve high coordination 

numbers, we propose re-envisioning these complexes as main-group analogues of the organo-transition 

metal complexes used in modern homogeneous catalysis. The prospect of replacing expensive transition 

metals with cheaper and more abundant main-group metals in catalysis is an attractive one. Most catalysts 

operate via a ligand association-modification-dissociation cycle. To assess the potential catalytic activity, 

we have studied the interaction of unsaturated organic fragments such as alkenes, dienes, ketones and 

nitriles with organo-antimony complexes described earlier. The structure of new P-Sb complexes and 

their reactivity towards organic molecules will be presented. 

[dppm(SbCl3)2] [dppmSbCl2] + [dppmSbCl] 2+ [dppmSb] 3+ 

[1] C. A. Dyker, N. Burford, Chem. Asian. J., 2008, 3, 28. 

[2] E. Conrad, N. Burford, et. al., J. Am. Chem. Soc., 2009, 131, 5066. 

[3] E. Conrad, N. Burford, et. al., Chem. Commun., 2010, 46, 2465. 

[4] S. S. Chitnis, N. Burford, et. al., Chem. Commun., 2011, 47, 12331.

Poster 74 

163 


Synthesis and Structural Characterization of Indium-Oxygen-Organic 

Network Solids 

Glen G. Briand a , Marshall R. Hoey a , and Andreas Decken b 


a Department of Chemistry and Biochemistry, Mount Allison University, Sackville NB, Canada 

b Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada 

Indium oxide (In2O3) is a transparent conducting oxide with a number of applications in thin film form, 

such as liquid crystal displays, gas sensors, solar cells, light emitting diodes and other optoelectronic 

devices. It has been shown that molecule-based extended solids containing both inorganic and organic 

components represent materials with “tunable” physical properties, such as conductivity (Vaid et al. J. 

Am. Chem. Soc. 2008, 130, 14). Covalent bonding in these materials results in the high electron-hole 

mobilities of inorganic materials, while the molecular components allow for the fine-tuning of physical 

properties that is possible with organic materials. As an extension of or previous work with 

dimethylindium and -thallium chalcogenolates (Dalton Trans., 2010, 39, 3833; Eur. J Inorg Chem., 2011, 

2298; Eur. J. Inorg. Chem., 2011, 5430), we have studied the reaction of trimethylindium with various 

benezendiols and-triols to yield extended –(Me2IIn(OR)2InMe2)- networks. The syntheses and structural 

characterization of isolated materials will be discussed, as well as their potential as tunable conducting 

materials.

Exploring the Coordination Chemistry of Lead(II) Thiolates 

164 


Glen.G. Briand a , Teri J. Gullon a , Andrew D. Smith a , Anita S. Smith a and Gabriele Schatte b 


a Department of Chemistry and Biochemistry, Mount Allison University, Sackville NB, Canada 

b Saskatchewan Structural Sciences Centre, University of Saskatchewan, Saskatoon SK, Canada 

Despite the potential of heavy p-block metal (i.e. Tl, Pb, Bi) thiolates as interesting Lewis acids, little 

structural data for their coordination complexes have been reported. Previously, we have synthesized and 

structurally characterized a number of adducts of (2,6-Me2C6H3S)2Pb with monodentate, bridging, and 

chelating amine and phosphine ligands (Inorg. Chem., 2007, 46, 8625; Dalton Trans. 2004, 3515). This 

has resulted in the isolation of a variety of interesting bonding environments for lead(II). In an effort to 

increase the Lewis acidity at the lead(II) center, we have also prepared the cationic lead(II) thiolate {[4- 

(Me3N)C6H4S)6Pb3] 6+ using a zwitterionic ammonium thiolate ligand. This trinuclear species reacts with 

amine ligands to give mononuclear {[4-(Me3N)C6H4S]2Pb} 2+ ⋅Ln complexes (Polyhedron., 2012, 33, 171). 

To further explore this system, we have prepared (2-MeC6H4S)2Pb which incorporates less bulk at the 

lead(II) centre versus (2,6-Me2C6H3S)2Pb. We will discuss the preparation and solid-state structure of 

this complex, as well the coordination complexes resulting from its reaction with mono- and diamine 

ligands. 

RS 

RS 

L 

Pb: 

L 

RS 

RS 

L 

Pb: 

S' 

L 

RS 

SR 

Pb: 

S' 

Poster 75 

RS 

RS 

L 

Pb: 

N 

RS 

N 

Pb: 

SR 

P 

P 

SR 

Pb: 

SR 

RS 

RS 

P 

Pb:

Poster 76 

165 


Poly(methylenephosphine)s Containing Fluorescent Substituents as 

Chemosensors 

Benjamin W. Rawe, Cindy P. Chun, Derek P. Gates 

(brawe@chem.ubc.ca, dgates@chem.ubc.ca) 

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, 

Canada 

Polymeric chemosensors are practical materials used to detect potentially dangerous spieces pat very low 

concentration levels. [1] This presentation will illustrate how poly(methylenephosphine)s (PMPs), [2,3] 

bearing conjugated substituents can be used as "turn on" chemosensors (scheme 1). The polymers are 

prepared by anionic initiation of the phosphaalkene monomers (PA) featuring conjugated polyaromatic 

substituents. The unfunctionalized polymers (PMP-U) display low luminescence as the emission is 

quenched by the phosphorus lone pairs in the main chain of the polymer. Upon coordinating the 

phosphorus centres to a Lewis acid analyte (A) the emission from the polymers (PMP-A) substantially 

increase. The potential sensor applications for PMP's as well as the range of analytes that can be detected 

using florescence techniques will be outlined. 

Scheme 1: The polymerisation of phosphaalkenes and functionalization of 

poly(methylenephosphine)s to yield novel chemosensor materials. 

[1] Kim, H. N.; Guo, Z.; Zhu, W.; Yoon, J.; Tian, H. Chem Soc Rev.,2011, 40, 79-93 

[2] Tsang, C. W.; Yam, M.; Gates, D. P. J. Am. Chem. Soc., 2003, 125, 1480-1481 

[3] Bates, J. I.; Dugal-Tessier, J.; Gates, D. P. Dalton Trans., 2010, 39, 3151-3159

Poster 77 

Thermal Ring Closure of Aminopropylstannanes 

J. Pichler and F. Uhlig 

(johann.pichler@tugraz.at) 

Institute of Inorganic Chemistry, Graz University of Technology 

Stremayrgasse 9/V, A-8010 Graz, Austria 

166 


One of the main research interests of our group is focused on the development of novel, functionalized 

ring systems containing heavy group 14 elements. Such derivatives provide new synthetic applications in 

polymer chemistry, in catalysis as well as concerning biological activity. Investigations on the properties 

of currently synthesized organtin compounds containing amino propyl substituted side chains 1 lead to 

cyclostannazanes. They tend to be easily accessible via mild thermal ring closure reactions under reduced 

pressure (Figure 1). 

Figure 1 

The occurring protodearylation enables us to synthesize the target compounds in high yield and purity. 

All of these cyclostannazanes are characterized by state-of-the-art techniques.

Poster 78 

167 


Synthesis of Low Coordinate Group 13 and 14 Complexes Stabilized by 

Chelating Anionic Phosphine Ligands 

Jonathan W. Dube, Brian Malbrecht, Sarah Weicker and Paul J. Ragogna 

(jdube7@uwo.ca, pragogna@uwo.ca) 

Department of Chemistry and the Center for Materials and Biomaterials Research, Western University, 

1151 Richmond St, London, Ontario, N6A 5B7, Canada 

A majority of the isolated low valent group 13 and 14 compounds are prepared from hard anionic 

nitrogen based ligands, [1,2] while much less explored is the chemistry of the main group elements with the 

anionic phosphinoborate ligand class developed by Peters et al. [3-5] In this context, unique gallium, 

germanium, and tin complexes have been isolated from the reaction of 1 with the corresponding lower 

oxidation state main group halide. For Ge and Sn, 2 is formed in quantitative yields and the onwards 

reactivity was pursued. In the case of gallium, a novel base stabilized Ga2I2 2+ dimer (3) is prepared in 

yields that vary depending on the “GaI” preparation time. This finding prompted a study on the nature of 

“GaI” as a function of reaction time with solid-state characterization methods and model reaction 

outcomes being presented. 

[1] M. Assay, C. Jones, M. Driess, Chem. Rev. 2010, 111, 354. 

[2] R.J. Baker, C. Jones, Dalton Trans. 2005, 1341. 

[3] J.C. Thomas, J.C. Peters, J. Am. Chem. Soc. 2001, 123, 5100. 

[4] J.C. Thomas, J.C. Peters, Inorg. Chem. 2003, 42, 5055. 

[5] A.A. Barney, A.F. Heyduk, D.G. Nocera, Chem. Commun. 1999, 2379.

P-substituent Effects on the Insertion of Group 14 Carbenoids into 

Phosphorus–Halogen Bonds 

168 


Joseph K. West and Lothar Stahl 

(westjoek@gmail.com, lstahl@chem.und.edu) 

Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202-9024 USA 

The cyclic heterocarbenoids Me2Si(µ-N t Bu)2M (M = Ge and Sn) insert with varying rates into the 

phosphorus-chlorine bonds of aminochlorophosphines, arylchlorophosphines, and the thiophosphine 

PhP(S)Cl2. The reaction rates depend on both the steric bulk of the phosphines and the nature of the 

heterocarbenoid, the stannylene usually being significantly more reactive. The tin(IV) insertion products 

so created, however, also decompose much more rapidly than their germanium(IV) analogs. As is shown 

in the Scheme below, the decomposition of the insertion product can be significantly reduced, or even 

prevented, if the organic substituents on phosphorus bear greater steric bulk. Based on such qualitative 

observations, accompanied by detailed structural and kinetic data, plausible pathways for the insertion 

and decomposition mechanisms will be proposed. 

tBu N 

Si SnCl2 N 

tBu + 

(PhP) n 

n = 3Š5 

tBu N 

Si Sn 

N 

tBu PPh 2 

Cl 

Poster 79 

P 

Cl 

tBu N 

Si Sn 

N 

tBu P 

Cl 

tBu N 

Si Sn 

N 

tBu P 

Cl 

STABLE 

[1] Veith, M.; Grosser, M.; Huch, V. Z. Anorg. Allg. Chem. 1984, 513, 89–102. 

[2] Veith, M.; Gouygou, M.; Detemple, A. Phosphorus, Sulfur Silicon Relat Elem. 1993, 75, 183–186. 

[3] West, J. K.; Stahl, L. Organometallics 2012, 31, 2042–2052.

Poster 80 

169 


Metalloxanes Supported by Nitrogen Rich Heterocycles Comprising 

Chalcogen Donor Atoms 

Raymundo Cea-Olivares 1 , Christian Gil 2 , Mónica Moya-Cabrera 2, § 2, § 

, Vojtech Jancik 

(cea@unam.mx, monica.moya@unam.mx) 

1 

Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior s/n, Ciudad 

Universitaria, C.P. 04510, México 

2 

Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carr. Toluca-Atlacomulco 

Km 14.5, C.P. 50200, Toluca, Estado de México, México. § Academic staff from the Universidad Nacional 


Recently, we reported on the preparation of metal chalcogenide compounds bearing 4,5bis(diphenylphosphoranyl)-1,2,3-triazole 

ligands [H{4,5-(P(E)Ph2)2tz} (E = S(1), Se(2); tz =1,2,3triazole]. 

[1–3] The use of these types of ligands can lead to discrete structural arrangements for metals with 

a high tendency for oligomerization. 

Herein, we report on the preparation of lanthanide, aluminium and magnesium metalloxanes [(LnCp{4,5- 

(P(Se)Ph2)2tz})2(LnCp)(µ-O)] (Ln = Y (3), Sm(4)), [(Al(OH){4,5-(P(E)Ph2)2tz})3(µ-O)] (E = S (5), Se 

(6)) and [Mg{4,5-(P(S)Ph2)2tz}]2(µ-OH) (7) obtained from controlled hydrolysis of their corresponding 

chalcogenide derivatives. The structural analyses in solid state for 3 – 7 reveal that in all cases, the 

presence of a metalloxane moiety (M-O-M), as well as metal-chalcogen bonding (Figure 1). The degree 

of the aggregation observed for these compounds depends significantly on the size of the metal center as 

well as on the metal:ligand ratio employed for each reaction. 

Figure 1. Molecular structure of a metalloxane containing a Sm3O core. 

[1] Balanta-Diaz, J. A.; Moya-Cabrera, M.; Jancik, V.; Pineda-Cedeno, L. W.; Toscano, R. A.; Cea- 

Olivares, R., Inorg. Chem. 2009, 48, 2518–2525. 

[2] Alcantara-Garcia, J. Jancik, V.; Barroso, J.; Hidalgo-Bonilla, S.; Cea-Olivares, R.; Toscano, R. A.; 

Moya-Cabrera, M., Inorg. Chem. 2009, 48, 5874–5883. 

[3] Balanta-Diaz, J. A.; Moya-Cabrera, M.; Jancik, V.; Toscano, R. A.; Morales-Juarez, T. J.; Cea- 

Olivares, R., Z. Anorg. Allg. Chem. 2011, 637, 1346–1354.

170 


Definitive Structural Evidence for Phosphaamidines in Tautomeric C=P and 

C=N forms and Further Elaboration to Phosphaguanidines, 

Phosphinodiimines and Amidinophosphaalkenes 

L. Mokhtabad Amrei, a R. T. Boeré a and J.D. Masuda b 

(boere@uleth.ca) 

a Department of Chemistry & Biochemistry, University of Lethbridge, Lethbridge, AB T1T3M4 , Canada 

b The Maritime Centre for Green Chemistry and Department of Chemistry, St. Mary’s University, Halifax, 

NS B3H3C3, Canada 

P(III)-phosphaamidines replace one of the nitrogen atoms in an amidine by phosphorus. [1-3] Such 

phosphaamidines have been reported to exist in two tautomeric forms 1 and 2, but previously only the 

aminophosphaalkene form 1 has been structurally confirmed. [1] Here we report crystallographic evidence 

for two examples with the other tautomeric form 2. In addition, there is convincing spectroscopic 

evidence that 1,2(R=aryl;R 1 =R 2 =2,6-diisopropylphenyl) exist in solution as equilibrium mixtures. We 

also report on the chemical elaboration of the phosphaamidine functional group in related forms including 

the phosphaguanidine 3, P(III)-phosphinodiimines 4 and P(III)-amidinophosphaalkenes 5. 

R 

R 2 

P R 1 

NH 

R 

R 2 

N R 1 

PH 

R 3 

NH 

R 2 

N R 1 

PH 

Poster 81 

R P R 

R 1 

N 

R 2 

N 

R 3 

R N R 

1 2 3 4 5 

[1] R. T. Boere, M. L. Cole, P. C. Junk, J. D. Masuda, G. Wolmershauser, Chem. Comm. 2004, 2564- 

2565. 

[2] X. F. Li, H. B. Song, C. M. Cui, Dalton Trans. 2009, 9728-9730. 

[3] M. Y. Song, B. Donnadieu, M. Soleilhavoup, G. Bertrand, Chem.-Asian J. 2007, 2, 904-908. 

[4] J. D. Masuda, D. W. Stephan, Dalton Trans. 2006, 2089-2097. 

[5] J. D. Masuda, D. W. Stephan, Can. J. Chem. 2005, 83, 477-484. 

R 1 

P 

R 2 

N 

R 3

Poster 82 

Scorpionate Ligands Based on Nickel or Cobalt 

Chalcogenophosphoranyltiazolates 

171 


Jesús Pastor-Medrano, a Erandi Bernabé-Pablo, b Marisol Reyes-Lezama, b T. Jesús Morales-Juarez, a 

Vojtech Jancik, b,§ 

(jmoralesj@uaemex.mx, vjancik@unam.mx) 

a) Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón Esq. Paseo 

Tollocan, C.P. 50120, Toluca, Estado de México, México. b) Centro Conjunto de Investigación en 

Química Sustentable UAEM-UNAM, Carr. Toluca Atlacomulco km. 14.5, C.P. 50200, Toluca, Estado de 

México, México. § Academic staff from the Universidad Nacional Autónoma de México 

The term scorpionate ligand was used for the first time for tris(pyrazolyl)borates, where the pyrazol units 

are usually substituted in the 4- or 3,5-positions to increase their solubility and steric bulk. [1] Many 

metallic complexes with these ligands have been prepared as models for enzyme active sites. Herein, we 

report on a scorpionate ligands formed in the reaction between Ni 2+ or Co 2+ and three equivalents of 4,5- 

(Ph2PE)2Tz (E = S, Se, Tz = 1,2,3-triazol). [2] The ligands are readily prepared in the form of a potassium 

salt and are air stable. The obtained compounds have been characterized by common analytical methods. 

Figure 1. Molecular structure of a potassium salt of the scorpionate ligand based on nickel and 

selenaphosphoranyltriazolate with thermal ellipsoids at 50 % probability only for noncarbon atoms. 

Hydrogen atoms have been omitted for clarity. 

[1] S. Trofimenko, Scorpionates: Polypyrazolylborate Ligands and Their Coordination Chemistry. World 

Scientific Publishing Company, 1999. 

[2] Jesús Pastor-Medrano, Erandi Bernabé-Pablo, Marisol Reyes-Lezama, T. Jesús Morales-Juarez, 

Vojtech Jancik, manuscript in preparation.

172 


On the Structural Diversity of Aminotrialkoxides of Tin and Related Tin-Oxo 

Clusters 

T. Zöller, Ljuba Iovkova-Berends, Christina Dietz and K. Jurkschat 

(thomas.zoeller@tu-dortmund.de) 

Lehrstuhl für Anorganische Chemie II der Technischen Universität Dortmund, 

Otto-Hahn-Str. 6, 44227 Dortmund, Germany 

Metal(IV)-derivatives of triethanolamines are called Metallatranes [1] and hold great potential as Lewisacid 

catalysts. [1,2] Organostannatranes N(CH2CH2O)3SnR are known for a long time [1a] but purely 

inorganic representatives that lack any tin-carbon bond are scarce. [3] Our motivation for the synthesis of 

such compounds results from their non-toxicity and their potential as delayed action catalysts in the 

polyurethane formation. [2c] Here we report the syntheses and structures of tin aminotrialkoxides of the 

types A, B and C. [3] A systematic variation of the substituents X and R allows controlling the switchtemperature 

of the catalysts but gives also access to great structural diversity. These compounds hold, by 

partial hydrolysis, potential as precursors for unusual tin-oxo clusters of high nuclearity, such as D and E. 

O 

N 

Sn1 Sn2 

Sn3 Sn4 

D 

methyl groups are omitted 

Poster 83 

[1] a) J. G. Verkade, Coord. Chem. Rev., 1994, 137, 233. b) A. Singh, R. C. Mehrotra, Coord. Chem. 

Rev., 2004, 248, 101. 

[2] a) W. A. Nugent, J. Am. Chem. Soc., 1992, 114, 2768. b) F. Di Furia, G. Licini, G. Modena, R. 

Motterle, W. A. Nugent, J. Org. Chem., 1996, 61, 5175. c) J. Krause, S. Reiter, S. Lindner, A. 

Schmidt, K. Jurkschat, M. Schürmann, G. Bradtmöller, DE 102008021980, 2008. d) P. M. 

Gurubasavaraj, K. Nomura, Inorg. Chem. 2009, 48, 9491. e) S.-d. Mun et al., J. Organomet. Chem. 

2007, 692, 3519. 

[3] T. Zöller, C. Dietz, L. Iovkova-Berends, O. Karsten, G. Bradtmöller, A.-K. Wiegand, Y. Wang, V. 

Jouikov, K. Jurkschat, Inorg. Chem. 2012, 51, 1041. 

Sn3 

O 

Sn2 

N 

Sn1 

E

Poster 84 

Carbanionic Phosphoylide Dianion 

Sarah B. J. Dane, Vesal Naseri and Dominic S. Wright 

(sbjd2@cam.ac.uk) 

University of Cambridge, UK 

173 


Phosphorus ylides (Fig 1A) have become a classical tool for organic synthesis ever since the discovery 

that they could be used for olefination reactions by Wittig. Schildbauer [1] has extensively studies these as 

ligands but one elusive member of this family are dianions of the type [RP(CH2)3] 2- (Fig 1A), recently it 

has become possible to prepare and characterise them. 

Figure 1: (A) the structure of a classical phosohprus ylide. (B) the stutrure of [RP(CH2)3] 2- type dianions, 

(C) Isoelectronic p-block element imido and oxo-anions, isoelectronic with [RP(CHR')3] 2- dianions. 

Our interest in the phosphoylide dianions [RP(CHR')3] 2- , arises from their being valence-isoelectronic 

with a broad family of tripodal p-block element imido ligands of the type [RmE(NR)3] n- (Figure 1C), 

whose coordination chemistry has been investigated extensively in the past few decades. They are 

also isoelectronic with important classes of phosphorus oxo-anions, such as phosphonate anions [RPO3] 2- , 

which have broad applications in the synthesis of framework materials. DFT calculations show that 

[RP(CHR`)3] 2- are both σ-donors and π-acceptors: the σ-donor character is via the lone pairs on the CH2 

groups and the π-acceptor character is via the vacant σ* orbital of the P-C(R) bond. Reacting the 

phosphonium salt [PhP(CH3)3][I] with 3 eqv of t BuLi in thf gives [Li2{PhP(CH2)3}.2THF]2 (1) (Fig 2A). 

Transmetallations with Fe2I produced the hydride complex [{PhP(CH2)3Fe}4(µ4-H)] -. Li(thf)4 + (2) (Fig 

2B), a rare example of a [metal]4[µ4-H] compound. [2] 

A B 

Figure 2: (a) Structure of (1) [Li2{PhP(CH2)3}.2THF]2, (b) The tetranuclear hydride comples 

[{PhP(CH2)3Fe}4(µ4-H)] -. Li(thf)4 + (2) 

[1] W.C. Kaska, Coordination Chemistry Reviews, 1983, 48, 1-58 

[2] Robert J. Less, Vesal Naseri, Dominic S. Wright, Organometallics, 2009, 13, 3594-3596

Poster 85 

Diazastanna Four-Membered Rings 

174 


Tomas Chlupaty, 

Ales Ruzicka, Zdenka Padelkova and Hana Vankatova 

(tom-mail@seznam.cz) 


Pardubice, Studentska 573, CZ-532 10, Pardubice, Czech Republic 

Two possible pathways of forming of diazastanna four-membered rings via delocalization of π-electrons 

over the whole fundamental NCN skeleton of formamidinato/amidinato/guanidinato unit are known. [1] 

The first direct route is based on the nucleophilic addition of stannylenes (especially Lappert´s type) to 

starting N,N´-disubstituted carbodiimides. The second one is the substitution reaction of lithium (or other 

group 1 or 2 elements) precursor [2] with tin halide (in molar ratio 1:1/2:1) via salt elimination of lithium 

halide (or group 1 or 2 halide). These tin containing compounds can be used in further reactivity, for 

example oxidative addition on the metal center, [3] substitution of ligands and many many others. To the 

best of our knowledge the modern and sophisticated application is an activation of small (or larger) 

molecules by the help of formamidinato-/amidinato-/guanidinatotin cycles as a substrate. [4] The 

characterization of synthesized compounds was realized by XRD techniques and multinuclear NMR 

spectroscopy. 

Figure 1. The molecular structure of one of the compounds studied 

The authors would like to thank the Czech Science Foundation (grant nr. P207/12/0223) for financial 

support. 

[1] Nimitsiriwat, N.; Gibson, V. C.; Marshall, E. L.; White, J. P.; Daleb, S. H.; Elsegood, M. R. J. Dalton 

Trans. 2007, 4464; Sen, S. S.; Kritzler-Kosch, M. P.; Nagendran, S.; Roesky, H. W.; Beck, T.; Pal, 

A.; Herbst-Irmer, R. Eur. J. Inorg. Chem. 2010, 5304. 

[2] Chivers, T.; Fedorchuk, C.; Parvez, M. Inorg. Chem. 2004, 43, 2643. 

[3] Foley, S. F.; Yap, G. P. A.; Richeson, D. S. J. Chem. Soc., Dalton Trans. 2000, 1663. 

[4] Chlupaty, T.; Padelkova, Z.; DeProft, F.; Willem, R.; Ruzicka, A. Organometallics 2012, 2203.

Aldridge, K9 

Allan, Po63 

Baines, K5 

Baker, O47 

Barth, Po44 

Baumgartner, O18 

Beckmann, O1 

Bertrand, P1 

Bimbös, Po12 

Binder, Po59 

Boeré, O50 

Boeré, Po81 

Bolli, Po45 

Bourissou, K1 

Brand, Po5 

Braunschweig, P3 

Briand, Po41 



Chakrahari, O15 

Chitnis, Po73 

Chivers, O10 

Chlupaty, Po85 

Clyburne, Po1 

Cowley, Po61 

Cummins, K4 

Dane, Po84 

Dehnen, K3 

Diamond, Po22 

Dielmann, O36 

Dostál, Po19 

Driess, P8 

Dube, P33 

Dube, P78 

Dück, Po2 

Eironen, Po52 

Elder, Po32 

Espinosa, Po58 

Eußner, Po35 

Feierabend, Po11 

Ferkinghoff, Po4 

Fischer, O40 

Flock, Po25 

Forfar, Po23 

Frenking, K10 

Gabbaï, K12 

Gross, O4 

Presenting Author Index 

Gudat, O8 

Hasken, O55 

Hayward, O48 

Hazin, Po48 

Hering, Po68 

Hey-Hawkins, P6 

Horáček, Po9 

Hörl, Po7 

Houghton, Po71 

Hsieh, O19/Po65 

Hua, Po20 

Jäkle, O20 

Jambor, Po18 

Jancik, O51 

Jancik, Po29 

Jancik, Po82 

Jones, P7 

Jurschat, O53 

Karjalainen, Po54 

Keßler, O46 

King, Po55 

Klein, Po72 

Knapp, O28 

Knight, O22 

Kramer, Po3 

Kushida, Po56 

Kuwabara, Po39 

Laitinen, K2 

Lee, Po43 

Leitao, O14 

Less, O45 

Liu, C-W., O31 

Liu, S-Y., O38 

Lucas, Po37 

Lyčka, Po17 

Macdonald, C. O42 

MacDonald, E. Po34 

Mailman, withdrawn 

Majhi, Po57 

Masuda, O52 

Miyamoto, Po16 

Mori, O33 

Morrow, Po14 

Moya-Cabrera, O49 

Moya-Cabrera, Po80 

Myongwon Lee, Po70 

Naglav, Po67 

175 

Nagura, Po53 

Neilson, O46 

Nicholls-Allison, Po15 

Nordheider, Po31 

Olejnik, Po51 

Omae, O2 

Padelkova, Po66 

Passmore, O34 

Percival, O27 

Pichler, Po77 

Piers, P5 

Power, P4 

Preuss, O7 

Price, O32 

Priegert, Po60 

Radacki, Po64 

Ragogna, K11 

Rautiainen, O5 

Rawe, Po76 

Reed, K7 

Ritch, Po42 

Rivard, O30 

Roesler, O54 

Rosenberg, O24 

Ruzicka, O44 

Saito, M., O23 

Saito, M., Po21 

Saito, S., O29 

Sasamori, O21 

Scheer, O3 

Scheschkewitz, K6 

Schnepf, O37 

Schulz, O6 

Sekiguchi, P2 

Shang, Po6 

Slawin, Po36 

Streubel, O13 

Sugamata, Po13 

Swidan, Po8 

Tacke, O35 

Takaluoma, Po50 

ter Jung, Po27 

Tokitoh, O26 

Townsend, O12 

Tran, Po47 

Tsai, Po38 

Turek, Po49 


Uhlig, O43 

Vargas-Baca, O41 

Villalba Franco, Po24 

Villinger, Po10 

von Hänisch, O11 

Wahler, O9 

Wazir, O17 

Weigand, K8 

Weinert, Po28 

West, R., O25 

West, J., Po79 

Wilfling, Po26 

Wilson, Po69 

Wisian-Neilson, O39 

Wolf, O16 

Woollins, Po40 

Wright, K13 

Wrixon, Po62 

Zöller, Po30 

Zöller, Po83 

K = Keynote 

O = Oral 

P = Plenary 

Po = Poster

Program and Abstracts - University of Victoria

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