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Reactions of Silicon–Silicon Bonds, VI . Reductive Trichloroslilylation Reactions Leading to Alkyl‐ and Dialkylaminobis(trichlorosilyl)phosphanes
Author(s) -
Müller LutzPeter,
Zanin Andreas,
Du Mont WolfWalther,
Jeske Jörg,
Martens Reiner,
Jones Peter G.
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300312
Subject(s) - trichlorosilane , chemistry , triethylamine , steric effects , alkyl , lone pair , nmr spectra database , dimer , silicon , medicinal chemistry , crystallography , stereochemistry , molecule , spectral line , organic chemistry , physics , astronomy
Reactions of hexachlorodisilane and of trichlorosilane/triethylamine with alkyl‐and dialkylaminodichlorophosphanes RPCl 2 1a – i [R = i Pr: a ; (Me 3 Si) 2 CH: b ; R=1‐adamantly: c : R= t Bu: d ; R=Et 2 N: e ; R= i Pr 2 M: f ] furnish bis(trichlorosilyl)‐phosphanes RP(SiCl 3 ) 2 3a –f. However, when less bulky substituents are attached to the phosphorus atom, so that there is little steric crowding, the double reductive silylations leading from 1 to 3 are accompanied by side reactions and decomposition of 3 . Therefore, only 3b , 3c , 3d , and 3f wre isolated in a pure state. These compounds are more readily prepared by the; trichlorosilane/triethylamine method. 1 H‐, 31 P‐ and 29 Si‐Nmr spectra confirm their constitution. The structure of solid 3f , the first aminobis(trichlorosilyl)phosphane, was determined by X‐ray crystallography. 3f contains a phosphorus atom in a pyramidal environment surrounded by two silicon atoms and a planar nitrogen atom of the diisopropylamino group.