Elucidating Two Distinct Pathways for Electrocatalytic Hydrogen Production Using Co^II Pincer Complexes

Hydrogen gas is a sustainable energy source with water as the sole combustion product. As a result, efforts to catalyze H₂ production are pertinent and widespread. The electrocatalytic H₂ generating capabilities of two Co^II complexes, [Co(κ³ -2,6-{Ph₂ PNR}₂ (NC₅ H₃ ))Br₂ ] with R=H (I) or R=Me (II), were presented for a variety of proton sources including trifluoroacetic acid (TFA), acetic acid (AA), and trifluoroethanol (TFE). Cyclic voltammetry and controlled potential coulometry demonstrated that electrocatalysis from I and II occurred at two different potentials and are associated with different reduction processes. Density functional theory analysis provided insight into the identities of the catalyst and supported two distinct reaction pathways for electrocatalytic proton reduction. Specifically, stronger acids (e. g., AA, TFA) proceeded at -1.31 to -1.45 V through a M^I /M^III pathway while sources with higher pK_a values (e. g., TFE, H₂ O) generated hydrogen at -2.4 V via M⁰ /M^II ligand-assisted metal-centered reduction.