Iridium-Catalyzed Hydrogen Production from Hydrosilanes and Water

被引：47

作者：

Garces, Karin ^{[1
]}

Fernandez-Alvarez, Francisco J. ^{[1
]}

Polo, Victor ^{[2
]}

Lalrempuia, Ralte ^{[1
]}

Perez-Torrente, Jesus J. ^{[1
]}

Oro, Luis A. ^{[1
]}

机构：

[1] Univ Zaragoza, Fac Ciencias, CSIC, Dept Quim Inorgan,ISQCH, E-50009 Zaragoza, Spain

[2] Univ Zaragoza, Fac Ciencias, Dept Quim Fis, Inst Biocomp & Fis Sistemas Complejos BIFI, E-50009 Zaragoza, Spain

来源：

CHEMCATCHEM | 2014年 / 6卷 / 06期

关键词：

homogeneous catalysis; hydrogen generation; hydrolysis; iridium; water splitting; SI-H BOND; DIHYDROGEN COMPLEXES; HYDROLYTIC OXIDATION; POLY(SILYL ETHER)S; SILANE ALCOHOLYSIS; CARBON-DIOXIDE; HYDROSILYLATION; STORAGE; GENERATION; PHENYLACETYLENE;

D O I：

10.1002/cctc.201301107

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The iridium(III) complex [Ir(H)(CF3SO3)(NSiN)(coe)] (NSiN = fac-coordinated bis(pyridine-2-yloxy)methylsilyl, coe=cyclooctene) has been proven to be an effective catalyst precursor for hydrogen production from the hydrolysis of hydrosilanes at room temperature. The reaction performance depends both on the nature of the silane and the solvent. Interestingly, high turnover frequencies of around 10(5) h(-1) were obtained by using Et2SiH2 or (Me2HSi)(2)O as hydrogen sources and THF as the solvent. Moreover a mechanistic insight into this Ir-catalyzed hydrogen generation process, based on both theoretical calculations and NMR spectroscopy, is reported. The overall catalytic cycle can be viewed as a two-stage process that involves water-promoted Si-H bond activation followed by water splitting by a proton transfer.

引用

页码：1691 / 1697

页数：7

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