Electrochemical CO2 Reduction at Glassy Carbon Electrodes Functionalized by MnI and ReI Organometallic Complexes

The catalytic activities towards electrochemical CO2 reduction of two new rhenium and manganese complexes, namely fac‐Mn(apbpy)(CO)3Br (1) and fac‐Re(apbpy)(CO)3Cl (2) (apbpy=4‐(4‐aminophenyl)‐2,2′‐bipyridine), in both homogeneous and heterogeneous phases are compared. A glassy carbon electrode (GCE) surface has been functionalized with complexes 1 and 2 by two approaches: a) direct electrochemical oxidation of the amino group with formation of C−N bonds, and b) electrochemical reduction of the corresponding diazonium salts with formation of C−C bonds. The chemically modified GCEs show efficient conversion of CO2 into CO, with turnover numbers (TONs) about 60 times higher than those of the corresponding catalysts in homogeneous solutions, and in a much shorter time. Electrochemical CO2 reduction by two new Re and Mn catalysts in homogeneous and heterogeneous phases is studied. A glassy carbon electrode (GCE) surface is functionalized with the two complexes by two different methods, leading to the formation of C−N and C−C chemical bonds. The chemically modified GCEs show efficient conversion of CO2 to CO, with turnover numbers about 60 times higher than those of the corresponding catalysts in homogeneous solutions.