文献类型：期刊文献

英文题名：Mechanistic investigation of zinc-promoted silylation of phenylacetylene and chlorosilane: a combined experimental and computational study

作者：Huang, Pan[1];Liu, Zhen[1];Shao, Yunqi[1];Deng, Shifeng[2];Liu, Boping[3]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[3]South China Agr Univ, Coll Mat & Energy, Guangzhou 510642, Peoples R China

年份：2020

卷号：22

期号：40

起止页码：22935

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20204509470693);WOS:【SCI-EXPANDED(收录号:WOS:000581596800009)】；

基金：This work was sponsored by Shanghai Pujiang Program (18PJ1402500), and the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-18C01) at the East China University of Science and Technology. The authors acknowledge the Joint-PhD Program supported by the China Scholarship Council (CSC) for fellowships.

语种：英文

外文关键词：Aromatic hydrocarbons - Negative ions - Reaction intermediates - Chlorine compounds - Styrene

摘要：The zinc-promoted silylation method is of great importance to synthesize high-performance silicon-containing arylacetylene (PSA) resins in the industry. However, it is difficult to eliminate the accompanied by-product of terminal alkenes due to the lack of mechanistic understanding of the silylation. The initiation of zinc-promoted silylation is facilitated by the interaction between zinc and phenylacetylene. Our DFT calculations indicated that the intermolecular hydrogen transfer of phenylacetylene follows an ionic pathway, which generates a phenylacetylene anion and the corresponding alkene moieties on the zinc surface. The styrene by-product is observed in this stage, with its alkene moieties desorbing as radicals into the solvent under the high reaction temperature. Three possible intermediates of surface phenylacetylene anions were proposed including PhC=C-Zn, PhC=CZnCl, and (PhC=C)(2)Zn. These carbanion-zinc intermediates undergo an SN2 reaction with Me3SiCl to afford the alkynylsilane on the zinc surface, which is calculated to be the rate-determining step for the zinc-promoted silylation reaction.