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- W2083991845 abstract "Abstract The electron-transfer reaction kinetics of the Cr(OH 2 ) 6 2+ and V(OH 2 ) 6 2+ complexes with tetranuclear isomeric species of cobalt(III)-ammine complexes containing pyridine 2,6−, 3,5−, 2,4− and 2,5-dicarboxylate bridging ligands ( I – IV ) have been studied in solution with various hydrogen ion concentrations. Inner-sphere mechanism with attack of Cr(II) at a deprotonated remote pyridine nitrogen atom and subsequent electron transfer through the organic ligands are assigned for complexes II , III and IV . Due to steric hindrance by carboxylate groups, an outer-sphere mechanism is observed for complex I . The electron-transfer rates for complexes III and IV are 20–50 times faster than that in complex II , and are discussed in terms of the lowering of the energy barrier caused by a significant π orbital interaction of oxidant and reductant through a heterocyclic bridge ligand. Outer-sphere mechanism for reduction of I is assigned on the basis of a k Cr / k V ratio of 0.026. Reduction of complex II by V(II) is independent of [H + ] and proceeds by the outer sphere." @default.
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- W2083991845 date "1989-06-01" @default.
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- W2083991845 title "Kinetics of the electron-transfer reactions of tetranuclear isomeric species of cobalt(III)-ammine complexes with hexaaquochromium(II) and hexaaquovanadium(II) ions" @default.
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- W2083991845 doi "https://doi.org/10.1016/s0020-1693(00)80590-3" @default.
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