Electrochemical Oxidation of 4-Ethenyl[22]paracyclophane: Cyclic Voltammetry, Electrosynthesis of Polymers, Analysis by Liquid Chromatography, and Mass Spectrometry

✍ Scribed by Gollas, Bernhard ;Hesse, Ingrid ;Lotz, Ralf ;Pasch, Harald ;Speiser, Bernd ;Zagos, Ioannis

• Book ID: 102902601
• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 981 KB
• Volume: 1997
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.199719971112

✦ Synopsis

4-Ethenyl[2,

]paracyclophane is oxidized electrochemically at a platinum electrode in acetonitrile/O. 1 M tetra-n-butylammonium hexafluorophosphate. Its behavior in electro-oxidation is compared to that of styrene. Cyclic voltammetry proves diffusion controlled, direct one-electron oxidation of the hydrocarbon. The product of preparative scale electrolysis is analyzed by elemental analysis and various spectroscopic techniques. Bond formation occurs at the vinyl group, resulting in analogues of polystyrene. Polymers are sepa-rated on a reversed phase chromatography column, and on- line coupling to electrospray ionization mass spectrometry as well as a combination of size exclusion chromatography and MALDI-MS prove the formation of species up to the undecamer. The determination of the molecular product masses allows the assignment of the polymer end groups. A mechanistic hypothesis for the radical cation induced electropolymerization of the monomer is developed from the electrochemical and structural results.