Proton channels are essential to the high rates and low overpotentials of enzymes such as hydrogenase.  In this work, we attach a proton channel consisting of multiple proton relays to a nickel phosphine molecular catalyst, to investigate its role in enhancing rates or lowering overpotentials.  The proton channel consists of a pyridazine functional group and the resulting catalyst is able to operate at a low overpotential and utilizes water, instead of triethylamine, as the base for catalysis.  While more energetically efficient, the turnover rates are  ~ � of the rates of the parent catalyst, possibly due to the lower pKa of the pendant amine.  NMR studies are used to follow the rapid intramolecular proton movement from the nickel hydride and through the channel, and these studies, along with the observed rates, allow potential improvements in the proton channel to be proposed.

A proton channel allows a hydrogen oxidation catalyst to operate at a moderate overpotential with water as a base

245th National Meeting (2013)

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