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.
| Original language | English |
|---|---|
| Pages (from-to) | 14128-14132 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 54 |
| Issue number | 47 |
| DOIs | |
| Publication status | Published - Nov 16 2015 |
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Keywords
- CO reduction
- homogeneous catalysis
- hydricity
- iridium hydrides
- photochemistry
ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
Cite this
Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+ : Experimental and Computational Studies of their Hydricities, Interaction with CO2, and Photochemistry. / Garg, Komal; Matsubara, Yasuo; Ertem, Mehmed Z.; Lewandowska-Andralojc, Anna; Sato, Shunsuke; Szalda, David J.; Muckerman, James; Fujita, Etsuko.
In: Angewandte Chemie - International Edition, Vol. 54, No. 47, 16.11.2015, p. 14128-14132.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+
T2 - Experimental and Computational Studies of their Hydricities, Interaction with CO2, and Photochemistry
AU - Garg, Komal
AU - Matsubara, Yasuo
AU - Ertem, Mehmed Z.
AU - Lewandowska-Andralojc, Anna
AU - Sato, Shunsuke
AU - Szalda, David J.
AU - Muckerman, James
AU - Fujita, Etsuko
PY - 2015/11/16
Y1 - 2015/11/16
N2 - 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.
AB - 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.
KW - CO reduction
KW - homogeneous catalysis
KW - hydricity
KW - iridium hydrides
KW - photochemistry
UR - http://www.scopus.com/inward/record.url?scp=84954453602&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84954453602&partnerID=8YFLogxK
U2 - 10.1002/anie.201506961
DO - 10.1002/anie.201506961
M3 - Article
VL - 54
SP - 14128
EP - 14132
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 47
ER -