Reactions of an Isolable Dialkylsilylene with Carbon Dioxide and Related Heterocumulenes

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• 作者：Xupeng Liu ; Xu-Qiong Xiao ; Zheng Xu ; Xuemin Yang ; Zhifang Li ; Zhaowen Dong ; Chenting Yan ; Guoqiao Lai ; Mitsuo Kira
• 刊名：Organometallics
• 出版年：2014
• 出版时间：October 13, 2014
• 年：2014
• 卷：33
• 期：19
• 页码：5434-5439
• 全文大小：459K
• ISSN：1520-6041

文摘

An isolable dicoordinate dialkylsilylene, 2,2,5,5-tetrakis(trimethylsilyl)silacyclopentane-1,1-diyl (6), was found to react with CO₂ and ArN鈺怌鈺怷 (X = O, S) smoothly to give the corresponding bis(silyl)carbonate, 4-imino-1,3-dioxasiletane and 4-imino-1,3-dithiasiletane derivatives in high yields, respectively. The molecular structures of these products were determined by X-ray crystallography. All these reactions are parallel to those of a hypercoordinate silylene with 畏⁵-pentamethylcyclopentadienyl ligands, decamethylsilicocene, reported by Jutzi et al. and are suggested to involve similarly the formation of the corresponding Si鈺怷 doubly bonded compounds (X = O, S) at the initial steps. Mechanistic details of the multistep reaction of a model dialkylsilylene with CO₂ were investigated using DFT calculations.