Pulse radiolysis of acetonitrile solutions of tetra-n-butyl ammonium salts of 2- and 4-carboxybenzophenones [BP-COO−···N+(C4H9)4] were performed in order to generate directly the reduced forms of the benzophenone moieties within pre-formed ion pairs. In earlier studies on photochemical electron transfer reactions, ion pairs containing a tetraalkyl ammonium cation and a benzophenone radical anion were formed in an electron transfer to the triplet BP from a quencher consisting of a tetraalkyl ammonium salt of (phenylthio)acetic acid. In the current work, the [BP•−COO−···N+(C4H9)4] ion pairs were formed by direct reduction of the salts without the complication of a third moiety, i.e., the (phenylthio)acetic anion. The spectra and kinetic parameters of the radiolytically-reduced salts were compared to the behavior of reduced forms of the 2- and 4-COOH substituted benzophenones. The results from the pulse radiolysis and photochemistry were compared and explained in terms of the different structures of the ion pairs.
Research on Chemical Intermediates – Springer Journals
Published: Jun 11, 2009
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