Mechanistic investigation on hydrogenation and hydrosilylation of ethylene catalyzed by rhenium nitrosyl complex

详细信息    查看全文

• 作者：Lingjun Liu ; Siwei Bi ; Min Sun ; Xiangai Yuan ; Ning Zheng ; Ping Li
• 关键词：Hydrogenation ; Hydrosilylation ; Rhenium nitrosyl complex ; Ethylene
• 刊名：Journal of Organometallic Chemistry
• 出版年：2009
• 出版时间：15 September 2009
• 年：2009
• 卷：694
• 期：20
• 页码：3343-3348
• 全文大小：511 K

文摘

The mechanistic study for hydrogenation and hydrosilylation of ethylene catalyzed by a rhenium nitrosyl complex is carried out with the aid of density functional theory computations. The hydrogenation of ethylene is found to be available kinetically in which the oxidative addition of H₂ plays a role in decreasing the reaction barrier. For the case of hydrosilylation of ethylene, it is found the oxidative addition of HSiMe₃ cannot occur due to steric reasons, instead, a σ-bond metathesis process for reductive elimination of C₂H₅SiMe₃ is proposed. The major reason for the inaccessibility for the hydrosilylation is resulted from the fact that the oxidative addition of HSiMe₃ cannot give a more stable intermediate.