Hydride transfer to some initiators of cationic polymerization

TLDR: In this article, the hydride transfer from xanthene to stable carbenium salts with different cation electrophilities is investigated and the reaction is controlled by the absorption of the ions in the visible region of their electronic spectra.

Abstract: The hydride transfer from xanthene to stable carbenium salts with different cation electrophilities: 2,4′,4′'-trichlorotriphenylmethylhexachloroantimonate, triphenylmethylhexafluoroarsenate, triphenylmethylhexachloroantimonate, 4,4′,4′'-trimethyltriphenylmethylhexachloroantimonate and tropylium hexachloroantimonate is investigated. The reaction is controlled by the absorption of the carbenium ions in the visible region of their electronic spectra. The formation of the product of the reaction — triphenylmethane — is detected by gas chromatography and NMR spectroscopy. The rate constants and the reaction order are determined. The acceleration of the hydride transfer on UV-irradiation of the reaction mixture is shown.