Iridium catalyzed hydrogenation of CO2 under basic conditions-Mechanistic insight from theory

被引：95
作者：
Ahlquist, Marten S. G. [1 ]
机构：
[1] Royal Inst Technol, Sch Biotechnol, Dept Theoret Chem, SE-10691 Stockholm, Sweden
来源：
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2010年 / 324卷 / 1-2期
关键词：
DFT; Carbon dioxide; Iridium; Catalysis; Hydrogenation; Reduction; Formate; Base; Transition metal; Homogeneous; CONTINUUM DIELECTRIC THEORY; SOLVATION FREE-ENERGIES; CARBON-DIOXIDE; THERMOCHEMISTRY; DENSITY; MODEL; WATER;
D O I：
10.1016/j.molcata.2010.02.018
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) catalyzed hydrogenation of carbon dioxide under basic conditions was studied with density functional theory. It was found that the insertion of CO2 into an Ir-H bond proceeds via a two-step mechanism. The rate-limiting step was calculated to be the regeneration of the iridium(III) trihydride intermediate, and the overall barrier for the reaction was calculated to 26.1 kcal mol(-1). The formation of the iridium trihydride proceeds via formation of a cationic Ir(H)(2)(H-2) complex at which the base abstracts a proton from the dihydrogen ligand. (C) 2010 Elsevier B.V. All rights reserved.
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页码：3 / 8
页数：6
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