A dicationic Re bipyridine-type complex, -Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine )(CO)Cl hexafluorophosphate (), has been synthesized, and its electrochemical behavior under Ar and CO has been investigated. The presence of pendent tetra-alkylammonium cations induces an anodic shift in the electrocatalytic potential for CO reduction relative to structurally similar model complexes. The electrochemical mechanisms in anhydrous CHCN and in the presence of weak acids (water or trifluoroethanol) have been analyzed using cyclic voltammetry assisted by infrared spectroelectrochemistry and theoretical calculations. The dication enables catalysis at a diminished potential through Coulombic stabilization of the doubly reduced pentacoordinate species, its CO adduct, the hydroxide anion, and the conjugate base formed during acid-assisted C-OH bond cleavage of the metallocarboxylic acid to the metallocarbonyl and HO. The major reduction product is CO, but in the presence of trifluoroethanol, formate is also produced with 14% Faradaic efficiency.
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