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A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO₂ and a Proton Donor Promotes the Electrochemical Reduction of CO₂ to CO Catalyzed by a Rhenium Bipyridine-Type Complex

Haviv, Eynat, Azaiza-Dabbah, Dima, Carmieli, Raanan, Avram, Liat, Martin, Jan M. L., Neumann, Ronny
Journal of the American Chemical Society 2018 v.140 no.39 pp. 12451-12456
binding sites, carbon dioxide, carboxylic acids, catalysts, catalytic activity, electrochemistry, enzymes, histidine, hydrogen, hydrogen bonding, isotopes, ligands, moieties, nuclear magnetic resonance spectroscopy, oxygen, rhenium, thiourea
The electrochemical reduction of CO₂ has been extensively investigated in recent years, with the expectation that a detailed mechanistic understanding could achieve the goal of finding a stable catalyst with high turnover frequencies and low reduction potentials. In the catalytic cycle of the carbon dioxide hydrogenase enzyme, it has been suggested that the reduced metal center reacts with CO₂ to form a carboxylate intermediate that is stabilized by hydrogen bonding using a histidine moiety in the second coordination sphere. Using the well-known fac-Re(I)bipyridine(CO)₃Cl complex as a starting point, the bipyridine ligand was modified in the second coordination sphere with a thiourea tether that is known to form hydrogen bonds with carbonyl moieties. The resulting Re(I) catalyst was an excellent electrocatalyst for the selective reduction of CO₂ to CO, with a turnover frequency of 3040 s–¹. The binding of CO₂ to the thiourea tether was observable by ¹H NMR, and NOE experiments showed that the hydrogen atoms of the thiourea group were labile. Further experiments indicated that the thiourea moiety is also a local proton source and addition of an external proton source actually inhibits catalysis. The absence of a kinetic isotope effect was explained through DFT calculations that showed that the proton invariably jumps to the nearest CO₂ oxygen atom to form a metal–carboxylic acid without going through any minimum or transition state. EPR and NMR spectroscopies were used to identify the various reduced intermediates. Thus, the thiourea tether in the second coordination sphere can bind CO₂, stabilize carboxylic acid reaction intermediates, and directly act as a local proton source, leading to a significantly more active catalyst.