Steric and electronic effects in the bonding of N-heterocyclic ligands to transition metals

被引:409
作者
Cavallo, L
Correa, A
Costabile, C
Jacobsen, H
机构
[1] Univ Salerno, Dipartimento Chim, I-80184 Baronissi, SA, Italy
[2] Tulane Univ, Dept Chem, New Orleans, LA 70118 USA
关键词
carbenes; NHC-ligands; steric effects; electronic effects; QM/MM calculations;
D O I
10.1016/j.jorganchem.2005.07.012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
AT-heterocyclic (NHC) ligands constitute a new class of ligands that is going to commonly be used in organometallic chemistry. Nevertheless, detailed understanding of the bonding properties of these ligands to transition metals is scarce. In particular, a clear separation between steric and electronic effects is missing. Only in recent years combined experimental and computational studies on this topic have been performed. Here we review some advances in the field. We thus present a quantification of steric effects on the bond dissociation energy of various NHC-ligands from transition metals in complexes as Cp*Ru(NHC)Cl and Ni(CO)(3)(NHC). We further compare the steric requirements of various NHC ligands with the steric requirements of some phosphines. In the second part, we examine the different bonding modes that can contribute to the NHC-metal bond. We will review examples of metal-to-NHC back-donation (sigma -> 4d*) as well as of ligand-to-metal-to-NHC back-donation (pi -> d). (c) 2005 Elsevier B.V. All rights reserved.
引用
收藏
页码:5407 / 5413
页数:7
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