Combined ring inversion and side group rotation in geminal diphosphoryl substituted pyrrolidinoxyl radicals: ESR analysis of chemical exchange between four nonequivalent sites

Antal Rockenbauer, Anne Mercier, François Le Moigne, Gilles Olive, Paul Tordo

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The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found, for the 2,2-disubstituted compounds 2 and 3, dramatic changes in the spectra were observed as a function of the temperature. These changes were explained by a four-site chemical exchange model including both ring inversion and hindered rotation around the carbon - phosphorus bonds. For radical 3, the presence of additional 5,5-dimethyl substitution can completely block rotations around carbon - phosphorus bonds for certain ring geometries, while for other ring conformations chemical exchange still occurs through combined inversion - rotation processes. An effective two-site model composed of nonequivalent sites and a superposition model composed of a pair of exchanging conformers and a pair of nonexchanging conformers were used to simulate spectrum variations. A satisfactory fit was obtained over the entire temperature range investigated. From the temperature dependence of the exchange frequencies the potential barriers for ring inversion (27 kJ/mol), for combined inversion - rotation (11 kJ/mol), and for rotation around the carbon-phosphorus bonds (14 kJ/mol) were estimated.

Original languageEnglish
Pages (from-to)7965-7970
Number of pages6
JournalJournal of Physical Chemistry A
Issue number43
Publication statusPublished - Oct 23 1997


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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