Si(II) Cation-Promoted Formation of an Abnormal NHC-Bound Silylene and a cAAC-Silanyl Radical Ion.
Inorg Chem
; 60(10): 7143-7149, 2021 May 17.
Article
em En
| MEDLINE
| ID: mdl-33950667
ABSTRACT
The reaction of amidinatosilylene LSi()Cl [L = PhC(NtBu)2] with N-heterocyclic carbene IAr [C{N(Ar)CH}2, where Ar = 2,6-iPr2C6H3] and NaOTf in tetrahydrofuran (THF) facilely afforded a silicon(II) cation [LSi()-aIAr]+OTf- (1+OTf-), where IAr isomerizes to abnormal N-heterocyclic carbene aIAr, coordinating to the silicon(II) center. Its Ge homologue, [LGe()-aIAr]+OTf- (2+OTf-), was also accessed via the same protocol. For the formation of 1+, we propose that an in situ-generated Si(II) cation [LSi()]+ under the treatment of LSi()Cl with NaOTf may isomerize IAr in THF. In contrast, the replacement of IAr with cyclic alkyl(amino) carbene (cAAC) furnished a cAAC-silanyl radical ion [LSi(H)-cAAC]â¢+(LiOTf2)- [3â¢+(LiOTf2)-], which may undergo an abstraction of the H radical from THF. All of the products were characterized by nuclear magnetic resonance spectroscopy, electron paramagnetic resonance, and X-ray crystallography, and their bonding scenarios were investigated by density functional theory calculations. These studies provide new perspective on carbene-silicon chemistry.
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Base de dados:
MEDLINE
Tipo de estudo:
Guideline
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
China