TY - JOUR
T1 - Unexpected Formation of NHC-Stabilized Hydrosilylyne Complexes via Alkane Elimination from NHC-Stabilized Hydrido(alkylsilylene) Complexes
AU - Fukuda, Tetsuya
AU - Hashimoto, Hisako
AU - Tobita, Hiromi
N1 - Publisher Copyright:
© 2015 American Chemical Society.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2015/9/2
Y1 - 2015/9/2
N2 - N-heterocyclic carbene (NHC)-stabilized hydrosilylyne complex Cp∗(CO)2WSiH(MeIMe)2 (3a) (MeIMe = 1,3,4,5-tetramethylimidazole-2-ylidene) was formed by the reaction of an NHC-stabilized silylene complex Cp∗(CO)2(H)WSiH(MeIMe){C(SiMe3)3} (2a) with 1 equiv of MeIMe at 70 °C. In this reaction, HC(SiMe3)3 was unexpectedly eliminated from 2a. A C5Me4Et analogue of 3a, (C5Me4Et)(CO)2WSiH(MeIMe)2 (3b), was also synthesized by the same method, and the structure of 3b was confirmed by X-ray crystallography. Although the silicon center of 3b is coordinated by two NHCs, the length of the W-Si bond of 3b [2.363(4) Å] is as short as that of the shortest W=Si double bond (∼2.36 Å). These complexes, 3a and 3b, are the first examples of a base-stabilized silylyne complex having only a hydrogen on the silicon atom.
AB - N-heterocyclic carbene (NHC)-stabilized hydrosilylyne complex Cp∗(CO)2WSiH(MeIMe)2 (3a) (MeIMe = 1,3,4,5-tetramethylimidazole-2-ylidene) was formed by the reaction of an NHC-stabilized silylene complex Cp∗(CO)2(H)WSiH(MeIMe){C(SiMe3)3} (2a) with 1 equiv of MeIMe at 70 °C. In this reaction, HC(SiMe3)3 was unexpectedly eliminated from 2a. A C5Me4Et analogue of 3a, (C5Me4Et)(CO)2WSiH(MeIMe)2 (3b), was also synthesized by the same method, and the structure of 3b was confirmed by X-ray crystallography. Although the silicon center of 3b is coordinated by two NHCs, the length of the W-Si bond of 3b [2.363(4) Å] is as short as that of the shortest W=Si double bond (∼2.36 Å). These complexes, 3a and 3b, are the first examples of a base-stabilized silylyne complex having only a hydrogen on the silicon atom.
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U2 - 10.1021/jacs.5b06366
DO - 10.1021/jacs.5b06366
M3 - Article
AN - SCOPUS:84940972526
SN - 0002-7863
VL - 137
SP - 10906
EP - 10909
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 34
ER -