Studies on Mn complexes as electrocatalysts for proton reduction are limited. Mostly Mn complexes have been investigated for CO 2 activation. Hence, hydrogen production by three Mn complexes [(Mn(CO) 3 (μ-SN 2 C 7 H 5 )) 2 ] 1, [(Mn(CO) 3 (μ-S 2 NC 7 H 4 )) 2 ] 3 and [Mn 2 (CO) 7 (μ-S 2 NC 7 H 4 ) 2 ] 4 is reported in the paper. The complexes 1, 3 and 4 effectively catalyzed electro-chemical proton reduction in CH 3 CN with trifluoroacetic acid (TFA) as the proton source. Complexes 1, 3 and 4 displayed turnover frequency (TOF / s À 1 ) (overpotential, η / V) of 358 (0.83), 111 (0.79) and 102 (0.77), respectively for the catalytic process.

Innovative breakthroughs by designing cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources can help to solve the energy demand. An economically viable way could be the production of hydrogen. Designing noble metal-free catalysts can play an important role in the path towards sustainable hydrogen economy. Nobel metal catalysts are limited by their cost and scalability. In nature, the hydrogenases and photosystem II use iron,

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Mononuclear Mn(i) carbonyl complexes incorporating 2-mercaptobenzothiazole or 2-mercaptobenzimidazole and phosphaadamantane ligands were evaluated as electrocatalysts for the HER both in acetonitrile and acetonitrile/water.

The reaction of the tetranuclear iron complex [μ 4-Sulfido-bis{(μ-2-furylmethanethiolato) bis[tricarbonyliron](Fe-Fe)}] 1 with PPh 3 was explored. The reaction leads to the formation of the monosubstituted complex [Fe 2 (μ-2-furylmethanethiolate) 2 (CO) 5 (PPh 3)] 2. X-ray crystal structure has been reported for complex 2. Complexes 1 and 2 were found to be active catalysts for proton reduction. Complexes 1 and 2 showed comparable catalytic activity for proton reduction to dihydrogen.