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



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   

  1. 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
  • 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 Lia, Li Yanga, Lin Furonga, Tian Diyinga, Lei Qunfangb, Fang Wenjunb, Xie Hujuna   

  1. 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)(CNtBu)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