Hydrogen Evolving Mono‐nuclear Manganese Complexes with Carefully Positioned Pyridine Base Ligands

Enormous efforts have been made by the scientific community in the development of bio‐mimetic/bio‐inspired hydrogen‐evolving complexes as catalysts for an alternative hydrogen energy carrier and renewable energy sources. In this regard, new bio‐inspired mono‐nuclear Mn(I) carbonyl model complexes fac ‐[(Mn(CO) 3 (κ 2 ‐SN 2 C 7 H 5 )(κ 1 ‐PPh 2 Py))] 1 and fac ‐[(Mn(CO) 3 (κ 2 ‐S 2 NC 7 H 4 )(κ 1 ‐PPh 2 Py))] 2 with 2‐mercaptobenzimidazole (N,N) and 2‐mercaptobenzothiazole (S,N) ligands and a N‐based phosphine ligand (PPh 2 Py) have been synthesized, spectroscopically characterized and evaluated as electro‐catalysts for hydrogen generation. In contrast to related mono‐nuclear (N,N/S,N)−Mn−PPh 3 complexes, the newly introduced pyridine nitrogen atom of the PPh 2 Py ligand placed in an axial position in the second coordination sphere of the Mn(I) complexes, provides a first site for protonation and enables a fast intra‐molecular proton transfer to the central metal atom with a weaker acid. Theoretical DFT calculations enable a detailed picture of catalytic pathways, assign redox transitions and structural changes. Both the molecular complexes were tested as electro‐catalysts for hydrogen generation in CH 3 CN. Complexes 1 and 2 effectively catalyzed the electrochemical proton reduction with the weaker acetic acid as the proton source and displayed a turnover frequency ( TOF /s −1 ; overpotential, η/V) of 610; 1.02 and 615; 1.12, respectively. [Correction added on 25 July 2024, after first online publication: Preceding sentence was updated.] The computer‐aided design of dedicated proton transfer pathways from second coordination sphere ligands is thus able to allow a hydrogen evolution reactivity with a weaker acid (acetic acid).