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Matrix-isolation and electronic structure of vinyl-substituted silylenes and their complexes with bases [1]

✍ Scribed by Mitsuo Kira; Toyotaro Maruyama; Hideki Sakurai

Publisher
John Wiley and Sons
Year
1994
Tongue
English
Weight
827 KB
Volume
5
Category
Article
ISSN
1042-7163

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✦ Synopsis

Vinyl-substituted silylenes, 2,5-bis(methylene)-l -silacyclopentane-l ,l -diyl (1) and 2-methybne-1 -silacyclopentane-1 ,I -diyl (2), generated photochemically from the corresponding trisilanes in 3-methylpentane (3-MP) at 77 K, showed broad bands at 505 and 475 nm, respectively, which were assigned to the n(Si)-3p(Si) transition. The origin o f the red shift in the n(Si)-3p(Si) transition is ascribed to the significant lowering of the 3p(Si) orbital level caused by the vinyl substitution on the silylene; the relatively high-lying 3p(Si) orbital can interact more effectively with the antibonding m" orbital than with the bonding T orbital of the vinyl group. The absorption spectra for 1 and 2 in the presence of several bases in 3-MP glass matrix shifted significantly to blue due to the formation of the corresponding base complexes. Analysis of the spectral change of the silylenes upon complexation with bases was very constructive for the understanding of the structural characteristics of substituted silylenes.

INTROD UCTICIN

Generation, structure, and reactions of divalent silicon species, silylenes, have been extensively studied as important reactive intermediates both experimentally and theoretically . The electronic structure of silylenes has been discussed more Dedicated to Prof. Adrian Gibbs Brook on the occasion of his "To whom correspondence should be addressed. seventieth birthday.

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## Abstract Molecular‐orbital calculations have been performed for the conjugate base __cis__‐[Co(NH~3~)~4~(NH~2~)Cl]^+^ and __trans__‐[M(NH~3~)~4~(NH~2~)Cl]^+^ (M = Cr^III^, Co^III^, and Rh^III^), the hexacoordinated intermediates __cis‐__ and __trans__‐[Co(NH~3~)~4~(NH~2~)…Cl]^+^, the square‐pyra