Insights into the polymerization kinetics of some α-silylated thiophene oligomers

Autor: M. Wong Chi Man, Joël J. E. Moreau, Philippe Hapiot, J.P. Lere-Porte, Laurent Gaillon, Pierre Audebert
Rok vydání: 1997
Předmět:
Zdroj: Journal of Electroanalytical Chemistry. 435:85-94
ISSN: 1572-6657
DOI: 10.1016/s0022-0728(97)00116-2
Popis: Oxidation of several silylthiophene oligomers has been studied in dichloromethane and acetonitrile by cyclic voltammetry. Detailed mechanistic studies show that the oxidative coupling of silyloligothiophenes involves the carbon-carbon bond formation between two cation-radicals, as previously observed for other non-silylated oligothiophenes. The lifetimes of the cation-radicals are found to be dependent on the solvent, indicating a nucleophilic assistance to the CSi cleavage. This behavior is in agreement with a reversible coupling step leading to the formation of a dimeric cation followed by the irreversible cleavage of the CSi bond. Evidence for the existence of an equilibrium between the monomeric cation-radical and an associated form (π-dimerization) has been obtained from the variation of the redox potential with the temperature and concentration for the most stable cation-radical.
Databáze: OpenAIRE
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