A molecular molybdenum–schiff base electro-catalyst for generating hydrogen from acetic acid or water

• The reaction of ligand, H2L and MoCl5 gives a Mo(VI) complex [MoL(O)2] 1.
• Complex 1 is capable of catalyzing hydrogen evolution from acetic acid and water.
• TOF reaches a maximum of 68 (DMF) and 356 (buffer, pH 6) moles/h, respectively.
• Sustained proton reduction catalysis occurs over a 69 h period and no decomposition of 1.

ABSTRACTThe reaction of 2-pyridylamino-N,N-bis(2-methylene-4-ethyl-6-tert-butylphenol) (H2L) and MoCl5 gives a molybdenum(VI) complex [MoL(O)2] 1, a new molecular electrocatalyst, which has been determined by X-ray crystallography. Electrochemical studies show that complex 1 can catalyze hydrogen evolution from acetic acid or aqueous buffer. Turnover frequency (TOF) reaches a maximum of 68 (in N,N-Dimethylformamide (DMF)) and 356 (in buffer, pH 6.0) moles of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) electrode to give H2 over a 69 h electrolysis period and no observable decomposition of the catalyst.

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