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Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H] + : Experimental and Computational Studies of their Hydricities, Interaction with CO 2 , and Photochemistry
Author(s) -
Garg Komal,
Matsubara Yasuo,
Ertem Mehmed Z.,
LewandowskaAndralojc Anna,
Sato Shunsuke,
Szalda David J.,
Muckerman James T.,
Fujita Etsuko
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201506961
Subject(s) - chemistry , denticity , excited state , hydride , ligand (biochemistry) , ground state , photochemistry , catalysis , cis–trans isomerism , crystallography , stereochemistry , crystal structure , metal , organic chemistry , biochemistry , physics , receptor , quantum mechanics , nuclear physics
We prepared two geometric isomers of [Ir(tpy)(ppy)H] + , previously proposed as a key intermediate in the photochemical reduction of CO 2 to CO, and characterized their notably different ground‐ and excited‐state interactions with CO 2 and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐ [Ir(tpy)(ppy)H] + , reacts with CO 2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH 3 CN/TEOA, a common reactive C‐trans ‐[Ir(tpy)(ppy)] 0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO 2 and produces CO with the same catalytic efficiency.