Abstract
In most of the oxidation-reduction reactions involving net electron transfer which have been studied, the experimental results yield only second order rates, and thus reflect the barrier to bringing reactants together as well as that for the electron transfer act itself. Recent advances in synthetic procedures make it possible to measure as an intramolecular or first order process, net electron transfer in complexes containing Co(III) and Ru(II) as oxidizing and reducing agents respectively for a wide variety of bridging groups. Systems in which the bridging groups mediate in electron transfer, as well as others, in which the bridging groups serve only to define the separation of the oxidizing agent and reducing centres become accessible to study. In a somewhat related class of reactions, a particular ligand in an oxidizing complex is converted by external means to a reducing agent, and the rate of reduction of the oxidizing metal ion by the damaged ligand is measured, as a first order process.
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