Mechanism of H₂ Production by Models for the [NiFe]-Hydrogenases: Role of Reduced Hydrides

The intermediacy of a reduced nickel–iron hydride in hydrogen evolution catalyzed by Ni–Fe complexes was verified experimentally and computationally. In addition to catalyzing hydrogen evolution, the highly basic and bulky (dppv)Ni(μ-pdt)Fe(CO)(dppv) ([1]0; dppv = cis-C2H2(PPh2)2) and its hydride derivatives have yielded to detailed characterization in terms of spectroscopy, bonding, and reactivity. The protonation of [1]0 initially produces...