Medium and Interfacial Effects in the Multistep Reduction of Binuclear Complexes with Robson-Type Li
June 29th, 2008 | by admin |Medium and Interfacial Effects in the Multistep Reduction of Binuclear Complexes with Robson-Type Ligand.
We present a combined experimental and computational approach to the modeling and prediction of reactivity in multistep processes of heterogeneous electron transfer. The approach is illustrated by the study of a Robson-type binuclear complex (-Cu(II)-Cu(II)-) undergoing four-electron reduction in aqueous media and water-acetonitrile mixtures. The observed effects of solvent, pH, buffer capacity, and supporting electrolyte are discussed in the framework of a general reaction scheme involving two main routes; one of them includes protonation of intermediate species. The main three problems are addressed on the basis of modern charge transfer theory: (1) the effect of the nature of reactant and intermediate species (protonated/deprotonated, bare or associated with supporting anion/solvent molecule) on the standard redox potential, the electronic transmission coefficient, and the intramolecular reorganization; (2) possible effect of protonation on the shape of the reaction free energy surfaces which are built using the Anderson Hamiltonian; (3) electron transfer across an adsorbed chloride anion. Quantum chemical calculations were performed at the density functional theory level.
Nazmutdinov RR, Roznyatovskaya NV, Glukhov DV, Manyurov I, Mazin VM, Tsirlina GA, Probst M.
Kazan State Technological University, K. Marx Str., 68 420015 Kazan, Russian Federation, Department of Electrochemistry, Faculty of Chemistry, Moscow State University, Leninskie Gory1- str.3, Moscow 119992, Russian Federation, and Institute of Ions Physics and Applied Physics, University of Innsbruck, A-6020 Innsbruck, Austria nazmutdi@kstu.ru, natasha@elch.chem.msu.ru.