期刊
INORGANIC CHEMISTRY
卷 55, 期 5, 页码 2284-2289出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b02649
关键词
-
资金
- Junta de Andalucia (Proyecto de Excelencia) [FQM-7079]
The mechanism of the vanadium-catalyzed deoxydehydration of glycols to alkenes by phosphanes (Chapman, G.; Nicholas, K. M. Chem. Commun. 2013, 49, 8199-8201) has been investigated with density functional calculations. Two alternative pathways, A and B, have been evaluated, and the three stages generally recognized in DODH processes have been identified: (i) activation of the diol by condensation on the vanadium complex and eventual formation of vanadium-glycolate, (ii) oxygen atom transfer to phosphane with reduction to a vanadium(III) species, and, finally, (iii) alkene extrusion from the vanadium-glycolate with regeneration of the starting catalyst. Pathway B, in which the reduction by the phosphane from vanadium(V) to V(III) species occurred before the diol condensation, is energetically preferred to pathway A, in which the diol activation preceded the oxo-transfer to the phosphane reductant.
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