Bonding analysis and the mechanisms on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH

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• 作者：Siwei Bi ; Yanyun Zhao ; Xiaojian Kong ; Xiaoran Zhao ; Qingming Xie
• 关键词：Alkoxy-bridged bis(silylene) complex ; Ring-opening ; Reaction mechanism ; Density functional calculation
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 出版时间：15 February 2008
• 年：2008
• 卷：693
• 期：4
• 页码：639-645
• 全文大小：350 K

文摘

The mechanistic study on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH is performed by using density functional theory. Four steps are predicted to be involved in the reaction, formation of hydrogen bonding between R and a MeOH, ring-opening of the Ru–Si1–O1–Si2 four-membered ring, formation of the six-membered ring, and the hydroxyl hydrogen migration to the metal center. It is found that the reaction is favorable thermodynamically and the hydroxyl hydrogen migration is the rate-determining step. Systematic variations of the structural parameters involved in the reaction mechanism are revealed, which revealed the relationship of the bond strength among Ru–Si, Si–O and O–H bonds.