Model acyclic peroxides of the Fenton probe 2-methyl-1-phenyl-2-propyl hydroperoxide (MPPH): kinetic probes for dissociative electron transfer

摘要

Electron transfer (ET) to the acyclic peroxides di-2-methyl-1-phenyl-2-propyl peroxide (DMPP) and tert-butyl 2-methyl-1-phenyl-2-propyl peroxide (BMPP) results in the concerted dissociative reduction of the O-O bond. These compounds are structurally related to the Fenton probe 2-methyl-1-phenyl-2-propyl hydroperoxide (MPPH), and devised as kinetic probes for ET reactions. Product studies and kinetic studies of both peroxides were performed using heterogeneous and homogeneous electrochemical techniques. The results of the kinetics were examined as a function of the driving force for Et using Saveant's dissociative Et theory. Besides providing a number of thermochemical parameters, analysis of the kinetics indicates that ET is non-adiabatic.