Cleavage of Carbon Dioxide by an Iridium-Supported Fischer Carbene. A DFT Investigation

被引：40

作者：

Brookes, Nigel J. ^{[1
]}

Ariafard, Alireza ^{[1
,3
]}

Stranger, Robert ^{[2
]}

Yates, Brian F. ^{[1
]}

机构：

[1] Univ Tasmania, Sch Chem, Hobart, Tas 7001, Australia

[2] Australian Natl Univ, Dept Chem, Canberra, ACT 0200, Australia

[3] Islamic Azad Univ, Cent Tehran Branch, Fac Sci, Dept Chem, Tehran, Iran

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 16期

基金：

澳大利亚研究理事会;

关键词：

DENSITY-FUNCTIONAL THEORY; EFFECTIVE CORE POTENTIALS; MOLECULAR CALCULATIONS; HOMOGENEOUS CATALYSIS; METAL-COMPLEXES; CO2; REDUCTION; ACTIVATION; APPROXIMATION; HYDROGENATION;

D O I：

10.1021/ja809320x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of CO(2), OCS, and PhNCO with an iridium-supported Fischer alkoxycarbene has been investigated with density functional theory. We have confirmed the mechanism for the important CO(2) reaction and successfully rationalized the selective cleavage of the CS and CN bonds in OCS and PhNCO. Armed with this information we have used our model to predict that the same iridium system will preferentially cleave the CS bond in methyl thiocyanate (MeNCS) rather than the CN bond. The formation of the iridium-supported carbene itself has also been investigated and a fascinating autocatalytic mechanism has been discovered which nicely fits the observed experimental behavior.

引用

页码：5800 / 5808

页数：9

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