Journal of the American Chemical Society, Vol.139, No.2, 738-748, 2017
Electrocatalytic Alcohol Oxidation with Ruthenium Transfer Hydrogenation Catalysts
Octahedral ruthenium complexes [RuX-(CNN)(dppb)] (1, X = Cl; 2, X = H; CNN = 2-aminomethyl-6-folylpyridine, dppb = 1,4-bis-(diphenylphosphino)butane) are highly active for the transfer hydrogenation of ketones with isopropanol under ambient conditions. Turnover frequencies of 0.88 and 0.89 s(-1) are achieved at 25 degrees C using 0.1 rnol % of 1 of 2, respectively, in :the presence of 20 equiv of potassium t-butoxide relative to catalyst. Electrochemical studies reveal that the Ru-hydride 2 is oxidized at low potential (-0.80 V versus ferrocene/ferrocenium, Fc(0/+)) via a chemically irreversible process with concomitant formation of dihydrogen. Complexes 1 and 2 are active for the electrooxidation of isopropanol in the presence of strong base (potassium t-butoxide) with an onset potential near -1 V versus Fc(0/+). By cyclic voltammetry, fast turnover frequencies of 3.2 and 4.8 s(-1) for isopropanol oxidation ate achieved with 1 and 2, respectively. Controlled potential electrolysis studies confirm that the product of isopropanol electrooxidation is acetone, generated with a Faradaic efficiency of 94 +/- 5%.