期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 64, 页码 17096-17104出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201803490
关键词
computational chemistry; homogenous catalysis; hydroformylation; kinetics; regioselectivity
资金
- European Union's Horizon 2020 research and innovation programme under the Marie Curie Sklodowska-Curie grant [642294]
A mechanistic model for the cobalt-catalyzed hydroformylation of propene, based on density functional theory and coupled cluster electronic structure calculations and transition state theory, is proposed to explain the experimentally observed reactivity and selectivity. The electronic structure calculations provide very accurate energies, which are used with transition state theory to compute rate constants; the kinetics of the network of coupled reactions are then modelled numerically for this organometallic reaction. The model accounts well for the dependence of rate on the concentrations of catalysts and reagents, and also on the temperature, and the agreement with experiment is improved still further upon making small adjustments to the ab initio calculated free energy values. The calculations provide detailed kinetic insight into the mechanism of hydroformylation and the role of various elementary steps in defining reactivity and selectivity.
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