Medium and Interfacial Effects in the Multistep Reduction of Binuclear Complexes with Robson-Type Ligand

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• 作者：Renat R. Nazmutdinov ; Nataliya V. Roznyatovskaya ; Dmitrii V. Glukhov ; Ibragim Manyurov ; Vladimir M. Mazin ; Galina A. Tsirlina ; Michael Probst
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：August 4, 2008
• 年：2008
• 卷：47
• 期：15
• 页码：6659-6673
• 全文大小：432K
• 年卷期：v.47,no.15(August 4, 2008)
• ISSN：1520-510X

文摘

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.