Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies

Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies

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Publisher
Springer Netherlands
Copyright
Copyright © 2009 by Springer Science+Business Media BV
Subject
Chemistry; Inorganic Chemistry ; Physical Chemistry ; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-009-0050-8
Publisher site
See Article on Publisher Site

Abstract

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.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jun 11, 2009

References

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