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Observation of a Cu(II)(2) (?-1,2-peroxo)/Cu(III)(2) (?-oxo)(2) equilibrium and its implications for copper-dioxygen reactivity.


ABSTRACT: Synthesis of small-molecule Cu2 O2 adducts has provided insight into the related biological systems and their reactivity patterns including the interconversion of the Cu(II) 2 (?-?(2) :?(2) -peroxo) and Cu(III) 2 (?-oxo)2 isomers. In this study, absorption spectroscopy, kinetics, and resonance Raman data show that the oxygenated product of [(BQPA)Cu(I) ](+) initially yields an "end-on peroxo" species, that subsequently converts to the thermodynamically more stable "bis-?-oxo" isomer (Keq =3.2 at -90?°C). Calibration of density functional theory calculations to these experimental data suggest that the electrophilic reactivity previously ascribed to end-on peroxo species is in fact a result of an accessible bis-?-oxo isomer, an electrophilic Cu2 O2 isomer in contrast to the nucleophilic reactivity of binuclear Cu(II) end-on peroxo species. This study is the first report of the interconversion of an end-on peroxo to bis-?-oxo species in transition metal-dioxygen chemistry.

SUBMITTER: Kieber-Emmons MT 

PROVIDER: S-EPMC4041702 | BioStudies | 2014-01-01

REPOSITORIES: biostudies

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