화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.119, No.11, 2722-2728, 1997
Marcus Theory of a Parallel Effect on Alpha for Hydride Transfer-Reaction Between NAD(+) Analogs
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 Bronsted plot with slope, a. The a 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.