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Title: Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry

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.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [5] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); PRESTO, Saitama (Japan); Kanagawa Univ., Yokohama (Japan)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Adam Mickiewicz Univ., Poznan (Poland)
  4. PRESTO, Saitama (Japan); Toyota Central R&D Labs., Inc., Aichi (Japan)
  5. Baruch College, CUNY, New York, NY (United States)
Publication Date:
OSTI Identifier:
1263904
Report Number(s):
BNL--111788-2016-JA
Journal ID: ISSN 1433-7851; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 47; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY CO2 reduction; homogeneous catalysis; hydricity; iridium hydrides; photochemistry