Isolation of Silacycles from the Reactions of a Monochlorosilylene LSi(:)Cl (L = PhC(NtBu)2) with Ethynyl Lithium Salts.
Inorg Chem
; 61(40): 15864-15870, 2022 Oct 10.
Article
em En
| MEDLINE
| ID: mdl-36178201
ABSTRACT
The reactions of amidinate silylene chloride LSi()Cl (L = PhC(NtBu)2) with TMS- and Ph-ethynyl lithium salts gave rise to silacycles 1 and 4, respectively. The formation of 1 and 4 may undergo cyclo-condensations of transient ethynylsilylene intermidiates and the activation of an amidinate backbone. The distinct structures of 1 and 4 may be derived from the different electronic or steric properties of ethynyl substituents, and their formation mechanisms were investigated by density functional theory (DFT) calculations. Moreover, a sequential reaction of LSi()Cl with BH3·SMe2 and TMSC≡CLi as well as a reaction of LSi()Cl with TMSC≡CLi under O2 exclusively obtained ethynylsilanes 2 and 3, respectively, which indicated that either blocking a lone pair of a Si(II) atom or oxidizing Si(II) to Si(IV) prevents the further conversion of ethynylsilylenes to silacycle 1. All products were characterized by NMR spectroscopy and X-ray crystallography.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
China