Highly Stereoselective Proton/Hydride Exchange: Assistance of Hydrogen Bonding for the Heterolytic Splitting of H2

被引：84

作者：

Friedrich, Anja ^{[2
]}

Drees, Markus ^{[2
]}

auf der Guenne, Joern Schmedt ^{[1
]}

Schneider, Sven ^{[2
]}

机构：

[1] Univ Munich, Dept Chem & Biochem, D-81377 Munich, Germany

[2] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 48期

关键词：

RUTHENIUM COMPLEXES; DIHYDROGEN COMPLEXES; MECHANISTIC ASPECTS; KETONES; HYDRIDE; DEHYDROGENATION; ACTIVATION; ALCOHOLS; CATALYST; REACTIVITY;

D O I：

10.1021/ja908644n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Graph Presented) The dihydrido amine complex [Ru(H)2PMe 3{HN(CH2CH2PiPr2) 2}] and H2O exhibit highly unusual, stereoselective H+/H- exchange, as derived using 1H 2D EXSY NMR spectroscopy. While HRuA rapidly exchanges with H2O [k = 337(20) L mol-1 s-1], no direct HRuB/H2O proton exchange was detected. Methylation of the pincer amine nitrogen results in unselective slow exchange of both hydrides with H2O. These results emphasize the important role of hydrogen bonding of N with Brønsted acids (e.g., water) for heteroloytic H2 activation with Ru-amide hydrogenation catalysts, which was confirmed computationally. © 2009 American Chemical Society.

引用

页码：17552 / 17553

页数：2

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