Oxygen Isotope Effects upon Reversible O_2-Binding Reactions:Characterizing Mononuclear Superoxide and Peroxide Structures

摘要

The characterization of intermediates in oxidation reactions of transition metals is a common goal in biological and inorganic chemistry needed to guide the development of new industrial catalysts that can use O_2 as a sacrificial oxidant.Such advances require improved capabilities for identifying metal-O_2 adducts as well as the mechanisms by which these species are formed.In this paper,we examine oxygen equilibrium isotope effects (~(18)O EIEs)on reversible reactions that give rise to peroxide (O_2~(2-))and superoxide (O_2~(1-))compounds.The EIEs reported here provide benchmarks for interpreting intermediates during transition-metal-mediated O_2 activation in a variety of natural and synthetic systems.