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

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....

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Bibliographic Details
Published in:Angewandte Chemie 2015-11, Vol.127 (47), p.14334-14338
Main Authors: Garg, Komal, Matsubara, Yasuo, Ertem, Mehmed Z., Lewandowska‐Andralojc, Anna, Sato, Shunsuke, Szalda, David J., Muckerman, James T., Fujita, Etsuko
Format: Article
Language:English
Subjects:
Carbon dioxide
Carbon monoxide
Chemical reduction
Chemistry
CO2‐Reduktion
Computer applications
Homogene Katalyse
Hydride
Iridium
Isomers
Photochemicals
Photochemie
Photochemistry
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Summary: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. Zwei geometrische Isomere von [Ir(tpy)(ppy)H]+ wurden hergestellt. Der Hydridcharakter dieser Komplexe und die Reaktivität gegenüber CO2 in ihrem Grundzustand und angeregten Zustand wurden mithilfe von Experimenten und Rechnungen untersucht.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201506961