Mechanism and activity of ruthenium olefin metathesis catalysts: The role of ligands and substrates from a theoretical perspective

被引:244
作者
Adlhart, C [1 ]
Chen, P [1 ]
机构
[1] Swiss Fed Inst Technol, Swiss Fed Inst Technol, Organ Chem Lab, CH-8093 Zurich, Switzerland
关键词
D O I
10.1021/ja0305757
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction mechanism of olefin metathesis by ruthenium carbene catalysts is studied by gradient-corrected density functional calculations (BP86). Alternative reaction mechanisms for the reaction of the "first-generation" Grubbs-type catalyst (PCY3)(2)Cl2Ru=CH2 (1) for the reaction with ethylene are studied. The most likely dissociative mechanism with trans olefin coordination is investigated for the metathesis reaction between the "first-" and the "second-generation" Grubbs-type catalysts 1 and (H(2)IMes)(PCY3)CI2Ru=CH2 (2) with different substrates, ethylene, ethylvinylether, and norbomene, and a profound influence of the substrate is found. In contrast to the degenerate reaction with ethylene, the reactions with ethyl vinyl ether and norbomene are strongly exergonic by 8-15 kcal/mol, and this excess energy is released after passing through the metallacyclobutane structure. While the metallacyclobutane is in a deep potential minimum for degenerate metathesis reactions, the energy barrier for the [2+2] cycloreversion vanishes for the most exergonic reactions. On the free energy surface under typical experimental conditions, the rate-limiting steps for the overall reactions are then either metallacyclobutane formation for 1 or phosphane ligand dissociation for 2.
引用
收藏
页码:3496 / 3510
页数:15
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