Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+: Experimental and Computational Studies of their Hydricities,Interaction with CO2, and Photochemistry |
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| Authors: | Dr Komal Garg Dr Yasuo Matsubara Dr Mehmed Z Ertem Dr Anna Lewandowska‐Andralojc Dr Shunsuke Sato Dr David J Szalda Dr James T Muckerman Dr Etsuko Fujita |
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| Affiliation: | 1. Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973‐5000 (USA);2. PRESTO, JST, 4‐1‐8 Honcho, Kawaguchi, Saitama 332‐0012 (Japan);3. Present address: Kanagawa University, Rokkakubashi 3‐27‐1, Kanagawa‐ku, Yokohama 221‐8686 (Japan);4. Present address: Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61614 Poznan (Poland);5. Toyota Central R & D Labs, Inc., Nagakute, Aichi, 480‐1192 (Japan);6. Department of Natural Science, Baruch College, CUNY, New York, NY 10010 (USA) |
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| Abstract: | 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. |
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| Keywords: | CO2 reduction homogeneous catalysis hydricity iridium hydrides photochemistry |
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