Chelating NHC Ruthenium(II) Complexes as Robust Homogeneous Hydrogenation Catalysts

被引：116

作者：

Gandolfi, Claudio ^{[1
]}

Heckenroth, Marion ^{[1
]}

Neels, Antonia ^{[2
]}

Laurenczy, Gabor ^{[3
]}

Albrecht, Martin ^{[1
]}

机构：

[1] Univ Fribourg, Dept Chem, CH-1700 Fribourg, Switzerland

[2] CSEM, XRD Applicat Lab, CH-2002 Neuchatel, Switzerland

[3] Ecole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland

来源：

ORGANOMETALLICS | 2009年 / 28卷 / 17期

关键词：

N-HETEROCYCLIC CARBENES; TRANSITION-METAL-COMPLEXES; OLEFIN-METATHESIS CATALYSTS; CROSS-COUPLING REACTIONS; H BOND ACTIVATION; ASYMMETRIC CATALYSIS; PINCER COMPLEXES; COORDINATION CHEMISTRY; REDUCTIVE ELIMINATION; PALLADIUM COMPLEXES;

D O I：

10.1021/om900356w

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of ruthenium(II) complexes have been prepared by using bidentate chelating N-heterocyclic carbene (NHC) ligands that feature different donor groups E (E=olefin, thioether, carboxylate, and NHC). Rigid coordination of all donor sites was concluded from NMR spectroscopy, and the electronic impact of the donor group was evaluated by electrochemical analyses. The chelating donor group had a strong influence on the activity of the metal center in catalyzing direct hydrogenation of styrene. A thioether group or a second NHC donor site essentially deactivates the metal center. Complexes comprising a NHC tethered with an olefin or a carboxylate group showed appreciable activity, though only the carboxylate-functionalized system proved to be a precursor for homogeneous hydrogenation. According to in situ high-pressure NMR analyses, complexes featuring a carboxylate chelating group are remarkably resistant toward reductive elimination even under strongly reducing conditions and may, therefore, be used repeatedly.

引用

页码：5112 / 5121

页数：10

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