Darstellung und Charakterisierung neuer niedrigkoordinierter ...

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Phosphorus Attached to a N-N Unit PN double bond) and 3_3a (with a formal PN bond order > 2) are fairly similar with 1.543 and 1.544 Å but elongated by 0.04 Å compared to that of 3_3b.In3_2a, the fairly short P-N bond can be explained by the intramolecular donoracceptor interaction of the p-LP at the adjacent N atom with the σ*(P-Cl) orbital similar to that in 3a or 3b, which is not possible in 3_3a (Figures 9, 11). Conclusions The reactions of diphenyl(chloro)phosphane and phenyl- (dichloro)phosphane with bis[lithium-tris(trimethylsilyl)-hydrazide] represent a fast and clean reaction resulting in the formation of hydrazinophosphanes 1 and 2 in high yields. Both species possess fairly small P-N bond lengths due to intramolecular donor-acceptor interactions and represent thermally stable (with respect to TMS-Cl elimination) compounds. Hence, 1 and 2 represent ideal precursors for further synthesis of compounds containing a NNP unit. Reaction with sulfur or selenium results in the formation of the oxidation products 4-7. Thermodynamic stabilization of the chlorine-containing systems appears in the important interaction between the nitrogen lone pair and the antibonding P-Cl σ* orbital. 37 All three steps of the reaction of bis[lithium-tris(trimethylsilyl)-hydrazide] with phosphorus trichloride represent exothermic reactions. Large activation barriers are responsible for the thermal stability of 3a ((TMS)2N(TMS)PCl2), linear 3_2a ((TMS)2NNP-Cl), and cyclic 3_2r with respect to intramolecular TMS-Cl elimination. Investigation of the potential energy surface of (TMS)NNP revealed that 3_3c (TMS-PNN) represents the global minimum. The analysis of the chemical bonds using the NBO partitioning scheme shows a strong polarization of the N-P and N-Si bonds. Acknowledgment. A.S. thanks Professor Dr. T. M. Klapötke (LMU München) for his generous support and advice. We also thank the Leibniz Rechenzentrum for a generous allocation of CPU time. We are indebted to Dr. K. Karaghiosoff and Professor Dr. A. Schmidpeter for helpful advice and Dr. M. Suter for measuring an X-ray data set. Supporting Information Available: Experimental details for the synthesis of the oxidized compounds ((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), (TMS)2N-(TMS)N-P(Se)Ph(Cl) (7)). X-ray crystallographic files in CIF format for the structure determinations of 1, 2, 4, and 8 and the calculated structural data, energies, IRCs, and frequency data of all of the investigated species (archive entries). This material is available free of charge via the Internet at http://pubs.acs.org or from the author. IC048286M Inorganic Chemistry, Vol. 44, No. 6, 2005 1751
5.2 Ein Triazadiphosphol Sebastian Herler, Peter Mayer, Jörn Schmedt auf der Günne, Axel Schulz, Alexander Villinger, Jan J. Weigand. Angew.Chem. 2005, 117(47), 7968 – 7971. In dieser Publikation wurde der Großteil der experimentellen Arbeiten von mir durchgeführt. Der eigene Beitrag liegt bei ca. 90%. 45
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 and 40: 5. Ausgewählte Original-Publikatio
Page 41 and 42: Mono-, Di-, and Tricoordinated Phos
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: Figure 12. PES of the intrinsic TMS
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
Page 105 and 106:
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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