Manganese Tricarbonyl Diimine Bromide Complexes as Electrocatalysts for Proton Reduction

Manganese tricarbonyl diimine complexes bearing pyridine and imidazole ligands have been prepared as electrocatalysts for proton reduction using acetic acid as the proton source. The electron-donor ability of the diimine ligand is found to play an important role in determining the efficiency of the electrocatalysts with [MnBr(pybz)(CO)₃] (pybz = 2-(2-pyridyl)benzimidazole) exhibiting the lowest overpotential (0.28 V) toward proton reduction. The [Mn(pybz)(CO)₃(MeCN)]⁺ cationic complex prepared via debromination of [MnBr(pybz)(CO)₃] by a silver salt has also been shown to catalyze proton reduction upon its electrochemical reduction. A neutral complex [Mn(pyridine-benzimidazolate)(CO)₃(MeCN)], which can be synthesized by reacting [MnBr(pybz)(CO)₃] with a strong base, has been detected using IR-SEC (infrared spectroelectrochemistry) as an intermediate species in the catalytic process. Using [MnBr(pybz)(CO)₃] as the model electrocatalyst, we have carried out density functional calculations to propose a proton reduction mechanism consistent with our experimental observations.