Carbonyl-Amplified Catalyst Performance: Balancing Stability against Activity for Five-Coordinate Ruthenium Hydride and Hydridocarbonyl Catalysts

被引：23

作者：

Beach, Nicholas J. ^{[1
]}

Blacquiere, Johanna M. ^{[1
]}

Drouin, Samantha D. ^{[1
]}

Fogg, Deryn E. ^{[1
]}

机构：

[1] Univ Ottawa, Dept Chem, Ctr Catalysis Res & Innovat, Ottawa, ON K1N 6N5, Canada

来源：

ORGANOMETALLICS | 2009年 / 28卷 / 02期

基金：

加拿大自然科学与工程研究理事会;

关键词：

N-HETEROCYCLIC CARBENE; BIS(DIHYDROGEN) COMPLEX RUH2(H-2)(2)(PCY(3))(2); GRUBBS METATHESIS CATALYST; TANDEM ROMP-HYDROGENATION; C-H BONDS; HOMOGENEOUS HYDROGENATION; OLEFIN METATHESIS; IN-SITU; PRIMARY ALCOHOLS; REACTIVITY;

D O I：

10.1021/om800778h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The activity of RuHCl(H-2)(PCy3)(L) 2a/b and RuHCl(CO)(PCy3)(L) 3a/b (a: L = PCy3; b: L = IMes; IMes = 1,3-dimesitylimidazol-2-ylidene) was assessed in hydrogenation of a range of molecular and polymeric olefins and in hydrogenation and isomerization of allylbenzene. Elevated temperatures and/or high H-2 pressures are required for efficient hydrogenation. Under these conditions, 3a/b outperform their dihydrogen analogues in both total productivity and turnover frequencies, despite theoretical and experimental evidence that the pi-acid CO ligand should be deactivating. A thermolysis study reveals that the CO complexes are much less susceptible to deactivation under conditions relevant to catalysis (also, the IMes derivative 2b is shorter-lived than 2a). We attribute the superior performance of 3a/b to their greater stability, which maintains higher concentrations of active catalyst than that possible for their H-2 analogues over the time scale of hydrogenation.

引用

页码：441 / 447

页数：7