Abstract
The mechanism of the bipyridylium comproportionation reaction has been determined using the redox states of methyl viologen (MV). The reaction, hitherto presumed to follow the stoichiometry MV2++ MV0→ 2 MV+, has been investigated using in situ electrochemical EPR and UV–VIS spectroscopy and been shown to proceed via an intermediate step forming a spin-paired radical cation dimer (MV)22+. Dimer dissociation occurs as a subsequent reaction stage.
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