Direct Determination of Electron-Transfer Properties of Dicopper-Bound Reduced Dioxygen Species by a Cryo-Spectroelectrochemical Approach.

ABSTRACT: Direct experimental determination of redox properties of superoxo (O₂^.- ) and peroxo (O₂^2- ) embedded in dicopper complexes bearing an unsymmetrical binucleating ligand was achieved using cryo-electrochemistry and cryo-spectroelectrochemistry in dichloromethane. Cyclic voltammetry for dicopper(I) (1⁺ ) oxidation to a Cu^I Cu^II mixed-valent species (1²⁺ ) under inert atmosphere at 193 K reveals slow heterogeneous electron-transfer kinetics, indicative of a large reorganization energy. Oxygenation of the dicuprous complex 1⁺ gives the bridged peroxo dicopper(II) species 3⁺ , which is reversibly oxidized to the superoxo complex 2²⁺ at E⁰ =0.11 V (vs. SCE) with a s

SUBMITTER: Lopez I 

PROVIDER: S-EPMC5783699 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature