TY - JOUR
T1 - Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+
T2 - Experimental and Computational Studies of their Hydricities, Interaction with CO2, and Photochemistry
AU - Garg, Komal
AU - Matsubara, Yasuo
AU - Ertem, Mehmed Z.
AU - Lewandowska-Andralojc, Anna
AU - Sato, Shunsuke
AU - Szalda, David J.
AU - Muckerman, James
AU - Fujita, Etsuko
PY - 2015/11/16
Y1 - 2015/11/16
N2 - 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 C-trans-[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.
AB - 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 C-trans-[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.
KW - CO reduction
KW - homogeneous catalysis
KW - hydricity
KW - iridium hydrides
KW - photochemistry
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U2 - 10.1002/anie.201506961
DO - 10.1002/anie.201506961
M3 - Article
AN - SCOPUS:84954453602
VL - 54
SP - 14128
EP - 14132
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 47
ER -