期刊
INORGANIC CHEMISTRY
卷 52, 期 21, 页码 12655-12660出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic401836n
关键词
-
资金
- Qatar National Research Fund (member of Qatar Foundation)
- NPRP [09-157-1-024, 09-143-1-022]
The thermal displacement of methyl acrylate from Fe(CO)(4)(eta(2)-CH2=CHCOOMe) by phosphine ligands is a relatively slow reaction requiring several hours at elevated temperatures. In the present study, it is observed that photolysis of the tetracarbonyl complex with UV light activates the process such that the reaction is complete within a few seconds. This rate enhancement is due to the formation of an intermediate eta(4) complex where the organic C=O and C=C units of methyl acrylate occupy axial and equatorial coordination sites on the Fe center, respectively, following photochemical CO loss. The displacement of methyl acrylate from this photolytically generated intermediate is facile with a remarkably low barrier of 8.7 kcal/mol. Density functional theory calculations support these experimental observations.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据