title: Oxygen isotope effects upon reversible O2-binding reactions: Characterizing mononuclear superoxide and peroxide structures.
abstract: Identifying intermediates in catalytic oxidation reactions requires the development of new probes of structure and mechanism. Reported here are proof-of-concept studies of oxygen (18O) isotope effects upon reversible O2-binding reactions of classic inorganic compounds. It is shown that the 18O equilibrium isotope effects may be used to differentiate structures where O2 is bound as a side-on peroxide ligand versus an end-on superoxide ligand. The application of 18O equilibrium isotope effects to the interpretation of 18O kinetic isotope effects and the study of O2 activation mechanisms is also discussed.
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Michael P
authors.initials: MP
authors.lastname: Lanci
authors.forename: Justine P
authors.initials: JP
authors.lastname: Roth
mesh_terms: D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D010103:Oxygen Isotopes / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D013481:Superoxides / Q000737:chemistry*
chemical_list: D010103:Oxygen Isotopes; D010545:Peroxides; D013481:Superoxides; D010100:Oxygen