Intermediates and Products of the Hexachlorodisilane Cleavage of Group 14 Element Phosphanes and Amines – Molecular Structure of Di-tert-butyl(trichlorosilyl)phosphane in the Gas Phase Determined by Electron Diffraction and ab Initio Calculations

Abstract

Reactions of dialkyl(trimethylsilyl)phosphanes RRЈPSiMe 3 (1:compounds R 3 SnSiCl 3 (19a-c) that decompose providing (R 3 Sn) 2 Si(SiCl 3 ) 2 (18a-c) and nBu 3 SnSi(SiCl 3 ) 3 (20c). R, RЈ = tBu; 3: R, RЈ = iPr; 5: R = iPr, RЈ = tBu) with Si 2 Cl 6 provide stable trichlorosilylphosphanes RRЈPSiCl 3 (2, 4, 6);Subsequently, compounds 19a-c decompose providing increasing amounts of 18a-c. Stannylphosphane 17b is also the reactions of silyl-and stannylamines of iPr 2 NMMe 3 (M = Si: 11; M = Sn: 12) with Si 2 Cl 6 , however, provide the stable cleaved by SiCl 4 leading to 6 with liberation of Et 3 SnCl, whereas 17b is formed from the reaction of 5 with Et 3 SnCl pentachlorodisilanylamine iPr 2 NSi 2 Cl 5 (13). Heating of 1 with the technical mixture Me 2 (Cl)SiSiCl 2 Me/(MeCl 2 Si) 2 under liberation of Me 3 SiCl. The suggestion of an extra stabilisation of P-Si bonds of trichlorosilylphosphanes was yields the stable silylphosphane tBu 2 PSiMe 2 Cl (8) and the disilanylphosphane tBu 2 PSi(Me)(Cl)Si(Me)Cl 2 (9). Methsubjected to direct evidence through the structure determination of the trichlorosilylphosphane tBu 2 PSiCl 3 (2) ylation of 9 with MeLi gave tBu 2 PSi 2 Me 5 10, which was isolated in a pure state. Reactions of tBu(iPr)PSiMe 3 (5) and in the gas phase by electron diffraction. This crowded molecule has a "normal" P-Si bond length of 225.0(12) pm; of organometal phosphanes tBu(iPr)PMR 3 (14: M = Ge, R = Me; 17a-c: M = Sn; R = Me, Et, nBu) with Si 2 Cl 6 were its C 1 symmetric conformation with both tBu groups and the SiCl 3 group twisted about 17°from the perfectly staggered monitored by 31 P, 29 Si, and 119 Sn NMR. -In the first step of these reactions, new tBu(iPr)PSi 2 Cl 5 (7) is formed. 7 is positions, and with each of the three groups tilted about 6°a way from each other, allows to reduce steric strain. accompanied by increasing amounts of tBu(iPr)PSiCl 3 (6) and Me 3 GeSiCl 3 (15)/(Me 3 Ge) 2 Si(SiCl 3 ) 2 (16) or traces of products of reductive C-trichlorosilylations, [3,4] we recently

Si-C Coupling Reaction of Hydrosilane with Activated Organic Compounds: A Facile Synthetic Route to Organosilicon Compounds

“…It is known that a silylene intermediate can be inserted into Si-Cl [52] or Si-H bonds [54] to form disilanes. It is known that a silylene intermediate can be inserted into Si-Cl [52] or Si-H bonds [54] to form disilanes.…”

Dichlorosilylene and dichlorogermylene transfer to alkylidenephosphanes

“…Experimentally, the hypothetic, P-Ge + Si-Si@P-Si + Ge-Si dismutation turned out to follow a more complex reaction path [15,20], because silyl-, germyl-and stannylphosphanes react with Si 2 Cl 6 in the first step by formation of pentachlorodisilanylphosphanes (R 2 PSi 2 Cl 5 ) and chlorosilanes, germanes or stannanes (transsilylation-like reactions at phosphorus, see Scheme 7). Pentachlorodisilanylphosphanes, however, act as reductive trichlorosilylation agents towards Me 3 GeCl and R 3 SnCl (R ¼ Me, Et, n-Bu), leading to the initially desired silylgermanes and silylstannanes R 3 ESiCl 3 (E ¼ Ge, Sn), that suffer from subsequent decomposition [19,20].…”

“…Pentachlorodisilanylphosphanes, however, act as reductive trichlorosilylation agents towards Me 3 GeCl and R 3 SnCl (R ¼ Me, Et, n-Bu), leading to the initially desired silylgermanes and silylstannanes R 3 ESiCl 3 (E ¼ Ge, Sn), that suffer from subsequent decomposition [19,20].…”