ISSN:
0749-1581
Keywords:
EPR
;
ENDOR
;
Galvinoxyls
;
Deuteriation
;
Dynamic processes
;
Biradicals
;
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The syntheses of tert-butylgalvinol with perdeuteriated tert-butyl groups and of 1,4-bicyclo[2.2.2]octanebisgalvinol are described. The EPR and ENDOR spectra of the corresponding galvinoxyl monoradicals reveal selective line broadening due to dynamic processes associated with hindered internal rotation of the phenoxy rings. Deuteriation of the central tert-butyl group in tert-butylgalvinoxyl gives rise to a substantial decrease of EPR line widths, allowing the determination of the kinetic parameters by means of line-shape analyses (ΔH≠ = 21.8 kJ mol-1, ΔS≠ = -32 J mol-1 K-1). The biradical 1,4-bicyclo[2.2.2]octanebisgalvinoxyl exhibits strong scalar and dipolar electron interactions (D = 97 MHz).
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1260260513
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