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Inorganics 2018, 6(1), 22;

A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen

Department of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USA
Author to whom correspondence should be addressed.
Received: 2 January 2018 / Revised: 19 January 2018 / Accepted: 22 January 2018 / Published: 25 January 2018
(This article belongs to the Special Issue N-Heterocyclic Carbene Metal Complexes: From Design to Applications)
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Re(pyNHC-PhCF3)(CO)3Br is a highly active photocatalyst for CO2 reduction. The PhCF3 derivative was previously empirically shown to be a robust catalyst. Here, the role of the PhCF3 group is probed computationally and the robust nature of this catalyst is analyzed with regard to the presence of water and oxygen introduced in controlled amounts during the photocatalytic reduction of CO2 to CO with visible light. This complex was found to work well from 0–1% water concentration reproducibly; however, trace amounts of water were required for benchmark Re(bpy)(CO)3Cl to give reproducible reactivity. When ambient air is added to the reaction mixture, the NHC complex was found to retain substantial performance (~50% of optimized reactivity) at up to 40% ambient atmosphere and 60% CO2 while the Re(bpy)(CO)3Cl complex was found to give a dramatically reduced CO2 reduction reactivity upon introduction of ambient atmosphere. Through the use of time-correlated single photon counting studies and prior electrochemical results, we reasoned that this enhanced catalyst resilience is due to a mechanistic difference between the NHC- and bpy-based catalysts. These results highlight an important feature of this NHC-ligated catalyst: substantially enhanced stability toward common reaction contaminates. View Full-Text
Keywords: CO2 reduction; photocatalysis; NHC-ligated complexes CO2 reduction; photocatalysis; NHC-ligated complexes

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Carpenter, C.A.; Brogdon, P.; McNamara, L.E.; Tschumper, G.S.; Hammer, N.I.; Delcamp, J.H. A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen. Inorganics 2018, 6, 22.

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