Quantifying the Donor-Acceptor Properties of Phosphine and N-Heterocyclic Carbene Ligands in Grubbs' Catalysts Using a Modified EDA Procedure Based on Orbital Deletion

被引：53

作者：

Antonova, Nadya S. ^{[1
]}

Carbo, Jorge J. ^{[1
]}

Poblet, Josep M. ^{[1
]}

机构：

[1] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43007, Spain

来源：

ORGANOMETALLICS | 2009年 / 28卷 / 15期

关键词：

TRANSITION-METAL-COMPLEXES; OLEFIN METATHESIS CATALYSTS; MECHANISM; BOND; CHARGE;

D O I：

10.1021/om900180m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The sigma-donation and pi-acceptor properties of phosphine and N-heterocyclic carbene (NHC) ligands in first- and the second-generation Grubbs' catalysts have been theoretically evaluated by means of a modified version of the energy decomposition analysis (EDA). According to the calculations, the NHC ligand is significantly more tightly bonded than the phosphine ligand as a consequence of the larger energetic contributions of the sigma-donation, pi-back-donation, and synergic effects. Despite its larger sigma-donor strength, the NHC ligand is a slightly poorer charge sigma-donor and better pi-acceptor than phophine, explaining the recently observed overall poorer charge donation of the NHC ligand.

引用

页码：4283 / 4287

页数：5

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