Abstract

The reaction of 2,3-bis(2-hydroxybenzylideneimino)-2,3-butenedinitrile (H 2 L) and Ni(CH 3 CO 2 ) 2 ·2H 2 O affords a nickel(II) complex [NiL] 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 from water. Turnover frequency (TOF) reaches a maximum of 193 (in DMF) and 574 (in buffer, pH 6) moles of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) electrode to give H 2 over a 42 h electrolysis period and no observable decomposition of the catalyst. • The reaction of Schiff base ligand, H 2 L and Ni(OAC) 2 ·2H 2 O affords a complex, [NiL] 1 . • Structure of 1 is determined by single crystal X-ray diffraction analysis. • Complex 1 is capable of generating hydrogen from acetic acid or water. • TOF reaches a maximum of 194 (DMF) and 574 (buffer, pH 6) moles/mole/h, respectively.

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