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A textbook of inorganic chemistry vol.VI part III Vanadium, by Sydney Marks

By Sydney Marks

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Extra info for A textbook of inorganic chemistry vol.VI part III Vanadium, Niobium, and Tantalum

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As with ferrocene, work terms can be ignored and internal contributions to the activation free energy calculated. The solvent dependence and thermodynamic parameters are in reasonable agreement with Marcus predictions using a dielectric continuum model though microscopic reactant-solvent interactions in forming the encounter complex cannot be accounted for. Problems with steric and non-adiabatic factors are also prevalent. 5. Cobalt(II) Oxidations(4o) of a number of cobalt and nickel macro cyclic complexes, and others, by [Co(H 20)6]3+ have been examined and though Marcus correlations are good, the evaluated self-exchange rate, 10- 12 M- 1 s-\ is very much lower than the measured rate of 5 M- 1 s-1.

Measurements of dielectric relaxation frequency have been used to obtain ac and dc conductivities, the latter of which lead to the rate of hopping ("site-transfer") conductivity. In the double salt K3 (Mn04)z, these data give the rate of the outer-sphere(7S) electron transfer reaction (35). A MnO:;- ... MnO~- ¢ MnO~- ... (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.

The electron transfer rates are relatively insensitive to structure once thermodynamic forces have been accounted for and are similar to corresponding rates for bridged electron transfer. In an attempt(30) to examine the chemical mechanism where electron transfer between two complexes takes place with a ligand radical intermediate, reactions of [Co(NH3)6]3+ with a series of pyridine-carboxylate radicals are compared with internal electron transfers in [Co(NH3)sL']2+ species where L is same pyridine-carboxylate ligand, this time coordinated directly to the cobalt(III) center.

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