期刊
INORGANIC CHEMISTRY
卷 61, 期 40, 页码 15864-15870出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01762
关键词
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资金
- NSF of China [21801055]
- Zhejiang Provincial Natural Science Foundation [LY20B020009]
- Hangzhou Leading Innovation and Entrepreneurship Team Project [TD2020015]
- open fund of the State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University [201916]
- National Center for High-Performance Computing of Taiwan
- Ministry of Science and Technology, Taiwan
The reactions of amidinate silylene chloride with TMS- and Ph-ethynyl lithium salts lead to the formation of different silacycles, indicating the involvement of cyclo-condensations of transient ethynylsilylene intermediates and the activation of an amidinate backbone. The structures of the silacycles are influenced by the electronic and steric properties of the ethynyl substituents.
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 center dot 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.
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