title: Medium and interfacial effects in the multistep reduction of binuclear complexes with robson-type ligand.
abstract: 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.
authors.affiliation: Kazan State Technological University, K. Marx Str., 68 420015 Kazan, Russian Federation. nazmutdi@kstu.ru
authors.forename: Renat R
authors.initials: RR
authors.lastname: Nazmutdinov
authors.forename: Nataliya V
authors.initials: NV
authors.lastname: Roznyatovskaya
authors.forename: Dmitrii V
authors.initials: DV
authors.lastname: Glukhov
authors.forename: Ibragim
authors.initials: I
authors.lastname: Manyurov
authors.forename: Vladimir M
authors.initials: VM
authors.lastname: Mazin
authors.forename: Galina A
authors.initials: GA
authors.lastname: Tsirlina
authors.forename: Michael
authors.initials: M
authors.lastname: Probst