Ruthenium hydride complexes of 1,2-dicyclohexylimidazol-2-ylidene

被引：46
作者：
Burling, S [1 ]
Kociok-Köhn, G [1 ]
Mahon, MF [1 ]
Whittlesey, MK [1 ]
Williams, JMJ [1 ]
机构：
[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
来源：
ORGANOMETALLICS | 2005年 / 24卷 / 24期
基金：
英国工程与自然科学研究理事会;
关键词：
d;
D O I：
10.1021/om050600c
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The mono and bis N-heterocyclic carbene (NHC) complexes Ru(ICy)(PPh3)(2)(CO)H-2 (1) and Ru(ICY)(2)(PPh3)(CO)H-2 (2) (ICy = 1,2-dicyclohexylimidazol-2-ylidene) were isolated from the reaction of Ru(PPh3)(3)(CO)H-2 with ICy at elevated temperature. X-ray crystallography revealed that I contains a trans arrangement of the PPh3 ligands with the ICy trans to hydride; in complex 2, the two ICy ligands are cis to one another. Both 1 and 2 undergo H/D exchange with D-2, as well as reacting rapidly with CO to give Ru(ICy)(PPh3(CO)(3) (3) and Ru(ICY)(2)(CO)(3) (4). Addition Of CO2 to solutions of 2 resulted in insertion into one of the Ru-H bonds to afford both the K-1- and K-2-formate complexes Ru(ICY)(2)(PPh3)(CO)(K-1-OCHO)H (5) and Ru(ICY)(2)(CO)(K-2-OCHO)H (6). Addition Of CO2 to 1 gave solely Ru(ICy)(2)(PPh(CO)-(K-2-OCHO)H (7). The product from reaction of ICy with Ru(PPh3)(3)HCl proves to be solvent dependent, generating two isomers of the mono-NHC complex Ru(ICy)(PPh3)(2)HCl (8a,b) in dichloromethane but the bis-NHC species Ru(ICY)(2)(PPh3)HCl (10) in THF. An agostic interaction between Ru and a beta-CH2 hydrogen of the My ligand is apparent both in the X-ray crystal structure of Sa and also in solution. This interaction is broken upon addition of CO, which yields Ru(ICy)(PPh3)(2)(CO)HCl (9). The molecular structure of the coordinatively unsaturated species 10 is devoid of any agostic bonding.
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页码：5868 / 5878
页数：11
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