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ELECTROCHEMICAL AND ESR KINETICS STUDIES OF ELECTRON TRANSFER IN THE SYSTEM BIS(η6-ARENE)CHROMIUM(0)/BIS(η6-ARENE)CHROMIUM(I)
Li, T. T.- T.,Brubaker, C.H.
, p. 223 - 234 (1981)
The self-exchange rates and activation parameters in the (η6-arene2Cr0/(η6-arene)2CrI systems (where arene = toluene, benzene, methoxylbenzene, biphenyl, ethylbenzoate and chlorobenzene) have been measured by the ESR line broadening technique in DMSO solvent.The one-electron reduction was investigated by cyclic voltammetry for the series of substituted complexes of (η6-arene)2CrI.A linear correlation was obtained between the measured E1/2 values and the sum of Hammett parameters, Σ?m.For a series of solvents, a linear relationship between log k (the exchange rate constant of (biph)2Cr0/+1) and (1/n2-1/Ds) where n2 and Ds are the optical and static dielectric constants of the solvent medium, respectively, has been observed.This linearity is predicted by Marcus treatment for outer-sphere electron transfer process.A correlation of the oxidation stability of sandwich compounds with their gas-phase ionization potentials is evident from a linear relationship between the oxidation half-potentials E1/2 (or sum of Hammett Σ?m values) and the gas-phase ionization potentials.
