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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

Journal Article · · Angewandte Chemie (International Edition)
 [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)
+ Show Author Affiliations

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) (SC-22)
OSTI ID:
1263904
Report Number(s):
BNL--111788-2016-JA; KC0304030
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 47 Vol. 54; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

Nickel Complexes of C-Substituted Cyclams and Their Activity for CO2 and H+ Reduction journal July 2017
Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex journal July 2018
Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex journal July 2018
Judicious Ligand Design in Ruthenium Polypyridyl CO 2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects journal July 2016
The elusive abnormal CO2 insertion enabled by metal-ligand cooperative photochemical selectivity inversion journal March 2018
Hydricity, electrochemistry, and excited-state chemistry of Ir complexes for CO 2 reduction journal January 2017
Coordination mode-induced isomeric cyclometalated [Ir(tpy)(nbi)Cl](PF 6 ) complexes: distinct luminescence, self-assembly and cellular imaging behaviors journal January 2017
A hexanuclear cobalt metal–organic framework for efficient CO 2 reduction under visible light journal January 2017
Visible-light CO 2 photoreduction of polyoxometalate-based hybrids with different cobalt clusters journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
homogeneous catalysis
hydricity
iridium hydrides
photochemistry