Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy-R)(CO)₃ Br] Complexes

The electrochemical behavior of fac-[Mn(pdbpy)(CO)₃ Br] (pdbpy=4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) (1) in acetonitrile under Ar, and its catalytic performances for CO₂ reduction with added water, 2,2,2-trifluoroethanol (TFE), and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V versus the standard calomel electrode (SCE) in CO₂ -saturated acetonitrile, reveal that the process selectivity is extremely sensitive to the acid strength, producing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV/Vis) study under Ar and CO₂ atmospheres shows that 1 undergoes fast solvolysis; however, dimer formation in acetonitrile is suppressed, resulting in an atypical reduction mechanism in comparison with other reported Mn^I catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO₂ reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)₃ Br] (ptbpy=4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst (2), bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO₂ .