Reaction Mechanism for the Alkoxylation of a Silyl Ligand in the Silyl- (silylene)ruthenium Complex: A Density Functional Theory Study

doi:10.6023/cjoc201410023

Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (3): 698-704.DOI: 10.6023/cjoc201410023 Previous Articles Next Articles

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甲硅烷基(硅烯)钌配合物中甲硅烷基甲氧基化反应机理的理论研究

周莉^a, 李阳^a, 林芙蓉^a, 田迪英^a, 雷群芳^b, 方文军^b, 谢湖均^a

a 浙江工商大学应用化学系杭州 310018;
b 浙江大学化学系杭州 310028

收稿日期:2014-10-16 修回日期:2014-12-10 发布日期:2015-01-05
通讯作者: 谢湖均 E-mail:hujunxie@gmail.com
基金资助:
国家自然科学基金(No. 21203166)和食品科学与工程浙江省重中之重一级学科开放基金(No. JYTsp2014111)资助项目.

Reaction Mechanism for the Alkoxylation of a Silyl Ligand in the Silyl- (silylene)ruthenium Complex: A Density Functional Theory Study

Zhou Li^a, Li Yang^a, Lin Furong^a, Tian Diying^a, Lei Qunfang^b, Fang Wenjun^b, Xie Hujun^a

a Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018;
b Department of Chemistry, Zhejiang University, Hangzhou 310028

Received:2014-10-16 Revised:2014-12-10 Published:2015-01-05
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21203166) and the Food Science and Engineering of Most Important Discipline of Zhejiang Province (No. JYTsp2014111).

The mechanism for the reaction of a silyl(silylene) ruthenium complex Cp*Ru(CO)(=SiMes₂)SiMe₃ with methanol was investigated via the density functional theory (DFT) calculations. The mechanism includes four steps. (1) The reaction initiates via the 1,2-addition of methanol to the Ru=Si bond, followed by Mes₂Si(OMe)H elimination to give Cp*Ru(CO)SiMe₃; (2) A methyl group of the silyl ligand migrates to Ru center via 1,2-Me migration, together with 1,2-addition of methanol, which is followed by the CH₄ release to form Cp*Ru(CO)Si(OMe)Me₂; (3) Step (2) repeats twice to give the fully alkoxylated product Cp*Ru(CO)Si(OMe)₃. (4) Coordination of isonitrile affords final product Cp*Ru(CO)(CN^tBu)Si(OMe)₃. The first step involving the 1,2-addition of methanol to the Ru=Si double bond is the rate-determining step for the whole reaction with a free energy barrier of 35.3 kcal/mol. The mechanism for the reaction of a silyl(germylene)ruthenium complex with methanol was also considered. The rate-determining step has relatively lower barrier of 31.8 kcal/mol in contrast to the silyl(silylene) ruthenium complex.

Key words: DFT calculation, reaction mechanism, silylene complex, germylene complex

Cite this article

Zhou Li, Li Yang, Lin Furong, Tian Diying, Lei Qunfang, Fang Wenjun, Xie Hujun. Reaction Mechanism for the Alkoxylation of a Silyl Ligand in the Silyl- (silylene)ruthenium Complex: A Density Functional Theory Study[J]. Chin. J. Org. Chem., 2015, 35(3): 698-704.

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甲硅烷基(硅烯)钌配合物中甲硅烷基甲氧基化反应机理的理论研究

Reaction Mechanism for the Alkoxylation of a Silyl Ligand in the Silyl- (silylene)ruthenium Complex: A Density Functional Theory Study

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