H2 and O2 Activation-A Remarkable Insight into Hydrogenase

This article summarizes the development of a range of organometallic, biomimetic analogues of [NiFe]hydrogenases and their employment in a new generation of H2-O2 fuel cells. It begins with a summary of O2-sensitive and O2-tolerant enzyme chemistry before detailing the properties and functionality of our biomimetic complexes, including: the first ever fully functional model, selective H2 and O2 activation, and the first catalyst using only common metals. These systems are centered on Ni-Fe, Ni-Ru, Ir-Ir, and Rh-Rh cores and use a range of ligands that all follow a set of design principles described herein.