Geometric and Electronic Structural Contributions to Fe/O 2 Reactivity

Abstract

Non-heme iron enzymes either activate substrate using a ferric center or dioxygen using a ferrous site. The latter had been extremely difficult to study. Thus we have developed new spectroscopic methodologies that provide geometric and electronic structural insight into the ferrous center, its interaction with cosubstrates for activation of dioxygen, and the nature of the intermediates generated in this reaction. The focus of this talk is on using nuclear resonance vibrational spectroscopy (NRVS) to define the geometric structure and variable temp. variable field magnetic CD (VTVH MCD) the electronic structure of Fe(III)-OOH and Fe(IV)=O intermediates, and the spin state dependence of their frontier MOs (FMOs) in controlling reactivity. [on SciFinder(R)]