Molybdenum Catalyzed Ammonia Borane Dehydrogenation: Oxidation State Specific Mechanisms

被引：89

作者：

Buss, Joshua A. ^{[1
]}

Edouard, Guy A. ^{[1
]}

Cheng, Christine ^{[1
]}

Shi, Jade ^{[1
]}

Agapie, Theodor ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 32期

基金：

美国国家科学基金会;

关键词：

CHEMICAL HYDROGEN STORAGE; TERPHENYL-DIPHOSPHINE COMPLEXES; DIHYDROGEN COMPLEXES; METAL; DIHYDRIDE; DINITROGEN; CHROMIUM; LIGAND; COORDINATION; DISPLACEMENT;

D O I：

10.1021/ja5059923

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Though numerous catalysts for the dehydrogenation of ammonia borane (AB) are known, those that release >2 equiv of H-2 are uncommon. Herein, we report the synthesis of Mo complexes supported by a para-terphenyl diphosphine ligand, 1, displaying metal-arene interactions. Both a Mo-0 N-2 complex, 5, and a Mo-II bis(acetonitrile) complex, 4, exhibit high levels of AB dehydrogenation, releasing over 2.0 equiv of H-2. The reaction rate, extent of dehydrogenation, and reaction mechanism vary as a function of the precatalyst oxidation state. Several Mo hydrides (Mo-II(H)(2), [Mo-II(H)](+), and [Mo-IV(H)(3)](+)) relevant to AB chemistry were characterized.

引用

页码：11272 / 11275

页数：4

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