End-On Copper(I) Superoxo and Cu(II) Peroxo and Hydroperoxo Complexes Generated by Cryoreduction/Annealing and Characterized by EPR/ENDOR Spectroscopy
Roman Davydov, Austin E. Herzog, Richard J. Jodts, Kenneth D. Karlin, Brian M. Hoffman
Abstract
complexes. During annealing to higher temperatures this state first undergoes internal electron transfer (IET) to form the end-on Cu(II) peroxo state, which is then protonated to form Cu(II)-OOH species. This is the first time these methods, which have been used to determine key details of metalloenzyme catalytic cycles and are a powerful tools for tracking PCET reactions, have been applied to copper coordination compounds.
Topics & Concepts
ChemistryElectron paramagnetic resonanceProtonationCopperAnnealing (glass)MetastabilityAdductCrystallographyPhotochemistryElectron transferIonNuclear magnetic resonanceOrganic chemistryPhysicsMaterials scienceComposite materialMetal-Catalyzed Oxygenation MechanismsMetal complexes synthesis and propertiesPorphyrin and Phthalocyanine Chemistry