Single electron transfer between selectfluor and chloride: A mass spectrometric and theoretical study

The reaction between 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis-tetrafluoroborate (selectfluor) and chloride has been studied experimentally and modeled computationally at the ab initio levels. Based on the interception experiments by electrospray ionization-mass spectrometry (ESI-MS), it is found that only 5,5-dimethyl-1-pyrroline N-oxide (DMPO) succeeds in trapping the chlorine free radical. This result indicates that the single electron transfer (SET) is likely to occur between selectfluor and chloride. According to the Marcus' theory, the activation and reaction free energies for this electron transfer have been calculated. The theoretical study shows that the electron transfer reaction is both thermodynamically and kinetically beneficial, which is consistent with the experiment. (C) 2013 Elsevier B.V. All rights reserved.