Hydrogen generation from carbon neutral sources is an important element of a multi-faceted strategy to meet growing global energy demands. Accordingly, renewed interest in H2 catalyst discovery has led to the creation of a variety of Fe, Ni and Co complexes that electrocatalyze H+ reduction. A particularly fascinating design element of emergent catalysts is the incorporation of a proton relay from a pendant acid-base group proximate to the metal center where H2 production occurs. In this study we have shown that utility of Nickel(II) Hangman Porphyrins have active sites for providing insight into the mechanism of H2 generation at the metal centers. An acid-base functionality is precisely positioned from a xanthene spacer. Mechanistic and electrochemical measurements have shown that in Nickel must be reduced beyond the formal oxidation state of NiI for H2 production to occur. In addition, kinetic studies have preformed to calculate the rate constants for proton delivery.

Electrochemical proton reduction with nickel hangman porphyrins

243rd National Meeting (2012)

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