Molecular Modeling of ruthenium alkylidene mediated olefin metathesis reactions. DFT study of reaction pathways

被引：90

作者：

Fomine, S ^{[1
]}

Vargas, SM ^{[1
]}

Tlenkopatchev, MA ^{[1
]}

机构：

[1] Univ Nacl Autonoma Mexico, Inst Invest Mat, CU, Mexico City 04510, DF, Mexico

来源：

ORGANOMETALLICS | 2003年 / 22卷 / 01期

关键词：

D O I：

10.1021/om020581w

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three possible reaction pathways have been studied for the Cl-2(PMe3)(2)Ru=CH2 and Cl-2(PCY3)(2)Ru=CH2 (Cy = cyclohexyl) mediated metathesis reaction of propylene by quantum-mechanical DFT calculations. It was found that in all cases the metathesis reaction proceeds via dissociative substitution of a phosphine ligand with propylene, giving a monophosphine complex. This tendency increases with ligand volume, and in the case of smaller PMe3 groups it is the entropy contribution to the reaction energetics that causes the monophosphine complex to participate in the metathesis reaction, according to the modeling data.

引用

页码：93 / 99

页数：7

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