Details

Autor(en) / Beteiligte

• Loke, Wen Liang James
• Guo, Wenzhuo
• Sohail, Muhammad
• Bengali, Ashfaq A.
• Fan, Wai Yip

Titel

Manganese Tricarbonyl Diimine Bromide Complexes as Electrocatalysts for Proton Reduction

Ist Teil von

• Inorganic chemistry, 2022-12, Vol.61 (50), p.20699-20708

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2022

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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.