期刊
ORGANOMETALLICS
卷 39, 期 1, 页码 18-24出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.9b00102
关键词
-
资金
- King Abdullah Univ. of Science and Technology (KAUST)
We studied the mechanism of the pyrrole synthesis catalyzed by a (PNP)-P-3-Mn pincer ligand system and show that a bifunctional double hydrogen transfer mechanism is favored over the alternative beta-hydride elimination. Both dehydrogenation and hydrogen-formation steps benefit from proton shuttles, with alcohol-mediated processes being consistently favored, leading to energy barriers that, in good agreement with the experimental results, are similar to those for the previously reported corresponding iridium-catalyzed process. We also show that the coordination of one potassium ion to the ligand lowers the energy barriers for the key steps. The overall rate-determining step is the regeneration of the catalyst with an energy barrier of 30.7 kcal/mol with potassium and 31.1 kcal/mol without potassium. Our results support the involvement and the importance of the aromatization/dearomatization paradigm in the reaction.
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