期刊
CHEMCATCHEM
卷 5, 期 6, 页码 1490-1496出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201200721
关键词
carbenes; carbon dioxide fixation; density functional calculations; hydrosilylation; reduction
资金
- Institute of Bioengineering and Nanotechnology (Biomedical Research Council, Agency for Science, Technology and Research, Singapore)
A metal-free reduction of carbon dioxide to methanol with N-heterocyclic carbenes (NHCs) as organocatalysts was achieved, which was conducted under ambient conditions with hydrosilane as the reducing reagent and the hydrogen source. Experimental results and density functional theory calculations indicated that the overall process involved a three-step cascade reaction. All three steps in the cascade reaction were found to be exothermic and were catalyzed by NHCs. The rate-determining step for the process was the first hydrosilylation step, which produced the formoxysilane intermediate, with an activation energy barrier of 19.6kcalmol-1. This observation explained the high tendency of the system to form the methoxide end product, with a hydrogen-transfer yield in excess of 95%.
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