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5.1 Mono-, Di- and Tri-Coordinated Phosphorus Attached to a N-N Unit: An Experimental and Theoretical Study Gerd Fischer, Sebastian Herler, Peter Mayer, Axel Schulz, Alexander Villinger, Jan J. Weigand. Inorg. Chem. 2005, 44(6), 1740 – 1751. In dieser Publikation wurde der Großteil der experimentellen Arbeiten von mir durchgeführt. Der eigene Beitrag liegt bei ca. 80%. 32
Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study † Gerd Fischer, Sebastian Herler, Peter Mayer, ‡ Axel Schulz,* Alexander Villinger, and Jan J. Weigand Department of Chemistry and Biochemistry, Ludwig-Maximilians-UniVersität München Butenandtstrasse 5-13 (Haus F), 81377 München, Germany Received December 7, 2004 Introduction N,N′,N′-[Tris(trimethylsilyl)]hydrazino-diphenylphosphane, (TMS)2N−(TMS)N−PPh2 (1), and N,N′,N′-[tris(trimethylsilyl)]hydrazino-phenyl(chloro)phosphane, (TMS)2N−(TMS)N−P(Cl)Ph2 (2), were obtained in the reaction of bis-[lithiumtris(trimethylsilyl)hydrazide] with PhnPCl3-n (n ) 1, 2). The structure and bonding of both species are discussed on the basis of experimentally observed (X-ray, Raman, NMR, and MS) and theoretically obtained data (B3LYP/ 6-31G(d,p), NBO analysis). Oxidation with sulfur and selenium results in the formation of (TMS)2N−(TMS)N−P(S)- Ph2 (4), (TMS)2N−(TMS)N−P(Se)Ph2 (5), (TMS)2N−(TMS)N−P(S)Ph(Cl) (6), and (TMS)2N−(TMS)N−P(Se)Ph(Cl) (7). Moreover, the thermal decomposition of N,N′,N′-[tris(trimethylsilyl)]hydrazine-dichlorophosphane, (TMS)2N− (TMS)N−PCl2 (3) and the reaction with magnesium have been investigated. The formation and molecular structure of the novel MgCl2(THF)2‚2Mg[(TMS)NP(O)2N(TMS)2](THF) (8) salt containing the hitherto unknown (TMS)NP- (O)2N(TMS)2 2− anion are discussed. DFT calculations (B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d,p)) are used to evaluate the bonding, ground-state structures, and energy landscape for the different isomers of 3: the thermodynamics and kinetics of the successive elimination of chlorotrimethylsilane (TMS−Cl) resulting in the formation of covalent azide analogues such as TMS−PNN or TMS−NNP. The low-coordination-number chemistry of the group 15 elements (N, P) has been developed extensively in the past thanks to the use of bulky groups. 1 It has been possible to characterize these reactive species because of their kinetic and thermodynamic stabilization by appropriate substitution. It was not until 1973 that Flick and Niecke were able to prove the existence of a phosphorus(III) compound with the structural feature of a phosphazene, -PdN-. 2 This first iminophosphane, a phosphazene with phosphorus in coordination number 2, was obtained in the reaction of bis- (trimethylsilyl)amino(difluoro)phosphane with lithium-bis- (trimethylsilyl)amide (eq 1) (Me 3 Si) 2 N-PF 2 + LiN(SiMe 3 ) 2 f (Me 3 Si) 2 N-PdSiMe 3 + LiF + Me 3 Si-F (1) * To whom correspondence should be addressed. E-mail: lex@ cup.uni.muenchen.de. Fax: +49-89-218077492. Phone: +49-89-218077772. † Dedicated to my father Dr. W. Schulz on the occasion of his 70th birthday. ‡ Performed X-ray structure analysis. (1) (a) Multiple Bonds and Low Coordination in Phosphorus Chemistry; Regitz, M., Scherer, O. J., Eds.; G. Thieme Verlag: Stuttgart, Germany, 1990. (b) Weber, L. Chem. ReV. 1992, 92, 1839. (c) Weber, L. Chem. Ber. 1996, 129, 367. Inorg. Chem. 2005, 44, 1740−1751 Shortly thereafter, phosphorus-nitrogen compounds with a two-coordinated phosphorus(III) atom represented a wellestablished group. 3-5 Because of the large number of stable low-coordinated phosphorus-nitrogen compounds, these species can no longer be regarded as exotic among the main group element compounds. This class of P-N compounds (2) Niecke, E.; Flick, W. Angew. Chem. 1973, 85, 586-587. Niecke, E.; Flick, W. Angew. Chem., Int. Ed. Engl. 1973, 12, 585-586. (3) (a) Scherer, O. J.; Kuhn, N. Angew. Chem. 1974, 86, 899. Scherer, O. J.; Kuhn, N. Angew. Chem., Int. Ed. Engl. 1974, 13, 811. (b) Niecke, E.; Scherer O. J. Nachr. Chem. Tech. 1975, 23, 395. (c) Scherer, O. J.; Kuhn, N. J. Organomet. Chem. 1974, 82, C3. (d) Scherer, O. J.; Kuhn, N. Chem. Ber. 1974, 107, 2123-2125. (e) Fleming, S.; Lupton, M. K.; Jekot, K. Inorg. Chem. 1972, 11, 2534. (f) Maryanoff, B. E.; Hutchins, R. O. J. Org. Chem. 1972, 37, 3475. (g) Thomas, M. G.; Kopp, R. W.; Schultz, C. W.; Parry, R. W. J. Am. Chem. Soc. 1974, 96, 2646. (h) Nöth, H.; Ullmann, R. Chem. Ber. 1976, 109, 1942. (i) Scherer, O. J.; Schnabl, G. Chem. Ber. 1976, 109, 2996. (j) Niecke, E.; Kröher, R. Angew. Chem. 1976, 88, 758. Niecke, E.; Kröher, R. Angew. Chem., Int. Ed. Engl. 1976, 15, 692. (k) Thomas, M. G.; Schultz, C. W.; Parry, R. W. Inorg. Chem. 1977, 16, 994. (l) Charbonnel, Y.; Barrans, J. Tetrahedron 1976, 32, 2039. (m) Schmidpeter, A.; Luber, J.; Tautz, H. Angew. Chem. 1977, 89, 554. Schmidpeter, A.; Luber, J.; Tautz, H. Angew. Chem., Int. Ed. Engl. 1977, 16, 546. (4) (a) Pohl, S. Chem. Ber. 1979, 112, 3159-3165. (b) Pohl, S. Angew. Chem. 1976, 21, 723. Pohl, S. Angew. Chem., Int. Ed. Engl. 1976, 11, 687-688. (5) Niecke, E.; Gudat, D. Angew. Chem. 1991, 103, 251-270. Niecke, E.; Gudat, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 0,217-237 and references therein. 1740 Inorganic Chemistry, Vol. 44, No. 6, 2005 10.1021/ic048286m CCC: $30.25 © 2005 American Chemical Society Published on Web 02/10/2005
Page 1 and 2: Darstellung und Charakterisierung n
Page 3 and 4: Erklärung Ich versichere hiermit a
Page 5 and 6: Der gesamten Arbeitsgruppe möchte
Page 7 and 8: Inhaltsverzeichnis 1. Aufgabenstell
Page 9 and 10: 1. Aufgabenstellung Ausgangspunkt d
Page 11 and 12: 2. Allgemeiner Teil 2.1. Abkürzung
Page 13 and 14: durch eine große strukturelle Viel
Page 15 and 16: Abbildung 5. Synthese N,N-Bis(trime
Page 17 and 18: 3.4 Binäre viergliedrige Phosphor(
Page 19 and 20: 4. Ergebnisse und Diskussion 4.1 Ei
Page 21 and 22: Strukturmerkmale formulieren: (i) M
Page 23 and 24: synthetisiert werden, weshalb sie s
Page 25 and 26: Abbildung 14. Molekülstruktur des
Page 27 and 28: werden, allerdings liegt das Iminoc
Page 29 and 30: 4.5. Eine ungewöhnliche Reaktion:
Page 31 and 32: 4.6. Lewis-Säure-assistierte Methy
Page 33 and 34: Die durchgeführten Austauschreakti
Page 35 and 36: Um das Dimer/Monomer-Gleichgewicht
Page 37 and 38: Bei Zugabe von nur einem Äquivalen
Page 39: 5. Ausgewählte Original-Publikatio
Page 43 and 44: (TMS)N-P(Cl2-n)Rn (m)1, 2) together
Page 45 and 46: molecules are rather constant and r
Page 47 and 48: Figure 1. Calculated molecular stru
Page 49 and 50: Figure 6. PES for the rearrangement
Page 51 and 52: Figure 12. PES of the intrinsic TMS
Page 53 and 54: 5.2 Ein Triazadiphosphol Sebastian
Page 55 and 56: Schema 1. Synthese der GaCl 3-Adduk
Page 57 and 58: Die ausschließliche Bildung von 2
Page 59 and 60: COMMUNICATION www.rsc.org/chemcomm
Page 61 and 62: [Mes* 2 2 t Bu 2 2H] + , 56 (16.4)
Page 63 and 64: P/N-Kationen Ein kationisches cycli
Page 65 and 66: gruppe C2/c mit vier Einheiten in d
Page 67 and 68: 5.5. An Unusual Reaction: a GaCl3-A
Page 69 and 70: GaCl3-Assisted Methyl/Chlorine Exch
Page 75 and 76: 5.6. Lewis-Acid-Assisted Methyl Exc
Page 77 and 78: Obviously, in case of the arsenic c
Page 79 and 80: It is interesting to note that in t
Page 81 and 82: Table 1. Selected bond lengths (in
Page 83 and 84: (8.35). 29 Si NMR (59.6 MHz, CD 2 C
Page 85 and 86: (1) a) Huisgen, R. in 1,3-Dipolar C
Page 87 and 88: Zuschriften Arsen-Stickstoff-Verbin
Page 89 and 90: Zuschriften liumatom eine von + 1.4
Page 91 and 92:
5.8 Cationic Cyclic Arsenic(III)Azi
Page 93 and 94:
exchange occurs in the cation (reac
Page 95 and 96:
H. Nöth, R. Ullmann, Chem. Ber. 19
Page 97 and 98:
[27] a) A. Hahma, E. Holmberg, N. H
Page 99 and 100:
Publikationen 30. Mono-, Di-, and T
Page 101 and 102:
Markus Kowalewski, Burkart Krumm, P
Page 103 and 104:
Z. Anorg. Allg. Chem. 2008, eingere
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Tetrahedron Lett. 2008, 49, 4901 -
Page 107 and 108:
Münchner Industrie-Tag, Oktober 20
Page 109:
Berufstätigkeit 09/2000 - 11/2000
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