Mechanistic insights into CO₂ conversion to CO using cyano manganese complexes

Without the use of a photosensitizer, [Mn(bpy)(CO)₃(CN)] (MnCN) can photochemically form [Mn(bpy)(CO)₃]^-, the active species for CO₂ reduction. While cases of the axial X-ligand dissociating upon irradiation of fac-[M(N-N)(CO)₃X] complexes (M = Mn or Re; N-N = bipyridine (bpy) ligand; X = halogen or pseudohalogen) are well documented, the axial cyanide ligand is retained when either [Mn(bpy)(CO)₃(CN)] or [Mn(mesbpy)(CO)₃(CN)], MnCN(mesbpy), are irradiated anaerobically. Infrared and UV-vis spectroscopies indicate the formation of [Mn(bpy)(CO)₂(MeCN)(CN)] (s-MnCN) as the primary product during the irradiation of MnCN. An in-depth analysis of the photochemical mechanism for the formation of [Mn(bpy)(CO)₃]^- from MnCN is presented. MnCN(mesbpy) is too sterically hindered to undergo the same photochemical mechanism as MnCN. However, MnCN(mesbpy) is found to be electrocatalytically active for CO₂ reduction to CO. Thus providing an interesting distinction between photochemical and electrochemical charge transfer.