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By M. V. Twigg (auth.), M. V. Twigg (eds.)

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Extra resources for Mechanisms of Inorganic and Organometallic Reactions: Volume 2

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The 88* excited state of [Re 2CIs]2is a strong oxidant(104) and gives a facile route to the powerful reductant [Re2CIsr. while near-diffusion-controlled oxidative quenching reactions of [*Ph(P 2 0 s)4Hst-, which is a stronger reducing agent than [*Ru(bipy h]2+, have been reported. 13. Metalloprotein Studies Oxidation and reduction (1 06) of cytochrome c at a gold electrode, modified by treatment with 4,4'-bipy, is close to reversible but shows additional potential-independent processes before and after the electron transfer.

79) Applied to the mixed-valence solid EU 3S4, it gives the rate of Eu(III) + Eu(II) electron transfer in good agreement with previous Mossbauer work. The V(V)/(IV) exchange occurs in partially reduced polyvanadic acid gels. 1). t See also footnote. p. 16. 22 1 • General and Theoretical The mixed-valence ion [P 2W IS vIVvi 0 62 ]10- exhibits rapid intramolecular electron hopping as shown by esr line broadening. Moreover, the esr spectra show partial delocalization of the electrons from V(IV) to the neighboring V(V), so that the complex must be classed as a borderline case between localized class II and delocalized class III.

Ref. 61). 6. Mixed-Valence Complexesf A review by Wong and Schatz(6Z) consolidates earlier work on the Piepho-Krausz-Schatz (PKS) vibronic coupling model, comparing this model with the Marcus-Hush and the various nonadiabatic models. The article, which is a model of clarity, relates the ground state properties of mixed-valence systems (localized versus delocalized cases), the optical properties (position and shape of the IT band), and the thermal electron transfer properties (rate and temperature dependence of activation energy) to two critical parameters'\ and e which correspond to the reorganization energy and the tunneling integral of the Marcus and semiclassical models.

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