Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [1](BF4)2. This complex comprises two bis(1‐methyl‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)methane (HBMIMurn:x-wiley:09476539:media:chem201905746:chem201905746-math-0001 ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [1](BF4)2 by either electrochemical or chemical means, one of its HBMIMurn:x-wiley:09476539:media:chem201905746:chem201905746-math-0002 ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [2](BF4) regenerates protonated complex [1](BF4)2. In presence of acetic acid in acetonitrile solvent [1](BF4)2 shows electrocatalytic proton reduction with a kobs of ≈200 s−1 at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIMurn:x-wiley:09476539:media:chem201905746:chem201905746-math-0003 ligand and a CoII−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.