Rate and equilibrium constants for hydride transfer from a series
of 1,3-dimethyl-2-substituted phenylbenzimidazolines to a pyridinium ion, a quinolinium ion, and a
phenanthridinium ion have been evaluated. Each
oxidizing agent gives a linear Brønsted plot with slope, α. The
α values vary systematically with the spontaniety
of the reactions. They are in reasonable agreement with the
predictions of modified Marcus theory. Their trend is
very accurately predicted, showing a parallel (Leffler−Hammond)
effect. These results make a multistep mechanism,
involving high energy intermediates, very unlikely.
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