A dinuclear triazenido–copper complex: A new molecular electro-catalyst for generating hydrogen from acetic acid or water

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The reaction of 1,3-bis[(4-chloro)benzene]triazene (HL) and CuCl2·2H2O affords a dinuclear triazenido–copper(II) complex [Cu2L4(NCCH3)] (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 water. Turnover frequency (TOF) reaches a maximum of 43 (in DMF) and 174 (in phosphate 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 H2 over a 72h electrolysis period and no observable decomposition of the catalyst.