Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry
Journal Article
·
· Angewandte Chemie (International Edition)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); PRESTO, Saitama (Japan); Kanagawa Univ., Yokohama (Japan)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Adam Mickiewicz Univ., Poznan (Poland)
- PRESTO, Saitama (Japan); Toyota Central R&D Labs., Inc., Aichi (Japan)
- Baruch College, CUNY, New York, NY (United States)
Here, 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.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC00112704
- OSTI ID:
- 1263904
- Report Number(s):
- BNL-111788-2016-JA; R&D Project: CO026; KC0304030
- Journal Information:
- Angewandte Chemie (International Edition), Vol. 54, Issue 47; ISSN 1433-7851
- Publisher:
- WileyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Cited by: 45 works
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