ELECTROCHEMICAL OXIDATION OF 4-ETHENYL[2(2)]PARACYCLOPHANE - CYCLIC VOLTAMMETRY, ELECTROSYNTHESIS OF POLYMERS, ANALYSIS BY LIQUID-CHROMATOGRAPHY, AND MASS-SPECTROMETRY

4-Ethenyl[22]paracyclophane is oxidized electrochemically at a platinu m electrode in acetonitrile/0.1 M tetra-n-butylammonium hexafluorophos phate. Its behavior in electro-oxidation is compared to that of styren e. Cyclic voltammetry proves diffusion controlled, direct one-electron oxidation of the hydrocarbon. The product of preparative scale electr olysis is analyzed by elemental analysis and various spectroscopic tec hniques. Bond formation occurs at the vinyl group, resulting in analog ues of polystyrene. Polymers are separated on a reversed phase chromat ography column, and online coupling to electrospray ionization mass sp ectrometry as well as a combination of size exclusion chromatography a nd MALDI-MS prove the formation of species up to the undecamer. The de termination of the molecular product masses allows the assignment of t he polymer end groups. A mechanistic hypothesis for the radical cation induced electropolymerization of the monomer is developed from the el ectrochemical and structural results.