Striking Differences in Properties of Geometric Isomers of [Ir(tpy)-(ppy)H]+: Experimental and Computational Studies of their Hydricities, Interaction with CO2, and Photochemistry

被引：52

作者：

Garg, Komal ^{[1
]}

Matsubara, Yasuo ^{[1
,2
]}

Ertem, Mehmed Z. ^{[1
]}

Lewandowska-Andralojc, Anna ^{[1
]}

Sato, Shunsuke ^{[2
,3
]}

Szalda, David J. ^{[4
]}

Muckerman, James T. ^{[1
]}

Fujita, Etsuko ^{[1
]}

机构：

[1] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA

[2] PRESTO, JST, Kawaguchi, Saitama 3320012, Japan

[3] Toyota Cent Res & Dev Labs Inc, Nagakute, Aichi 4801192, Japan

[4] CUNY Bernard M Baruch Coll, Dept Nat Sci, New York, NY 10010 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 47期

基金：

日本科学技术振兴机构;

关键词：

CO2; reduction; homogeneous catalysis; hydricity; iridium hydrides; photochemistry; EXCITED-STATES; REDUCTION; IRIDIUM; CATALYSTS; COMPLEX;

D O I：

10.1002/anie.201506961

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We prepared two geometric isomers of [Ir(tpy)(ppy)H](+), previously proposed as a key intermediate in the photochemical reduction of CO2 to CO, and characterized their notably different ground-and excited-state interactions with CO2 and their hydricities using experimental and computational methods. Only one isomer, C-trans-[Ir(tpy)(ppy) H]+, reacts with CO2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH3CN/TEOA, a common reactive Ctrans-[Ir(tpy)(ppy)](0) species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO2 and produces CO with the same catalytic efficiency.

引用

页码：14128 / 14132

页数：5

共 23 条

[1] Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles [J].