Type of Document	Dissertation
Author	Kozloski, Richard Peter
URN	etd-07152010-020336
Title	ESR investigation of some free-radical adducts.
Degree	PhD
Department	Chemistry
Advisory Committee	Advisor Name Title Dessy, Raymond E. Committee Chair Clifford, Alan F. Committee Member Field, Paul E. Committee Member Gibbs, Gerald V. Committee Member Ogliaruso, Michael A. Committee Member
Keywords	Free radicals (Chemistry)
Date of Defense	1977-01-15
Availability	restricted
Abstract The effect of steric strain on the esr hyperfine coupling constants of several free-radical adducts of perfluoropropene and perfluoro-2-butene were investigated. Silyl, hydroxyalkyl, thiyl and alkoxy free radicals, which were generated by photo-irradiation, reacted with these olefins to form free-radical adducts. Trends in the esr hfs were then looked for in each class of adducts. The thiyl and alkoxy radicals were found to be unsuitable for this type of study due to the low degree of steric strain produced by these species in the adducts. Trends toward higher a-Fβ/CF3 hfs and lower aFα hfs were observed for the silyl and hydroxyalkyl radical adducts as the steric strain in the adduct was increased. The ratio of the Fα to a-Fβ/CF3 hfs was shown to be a good measure of the degree of steric strain in these radical adducts. The possibility that the (Me3Si)2CHC(SiMe3)2 free radical, which has been reported to contain an "esr invisible" β-H, might be misidentified was investigated. Our conclusion was that the β-H is present and has not been replaced by a t-butoxy group.
Files	Filename       Size       Approximate Download Time (Hours:Minutes:Seconds)     28.8 Modem   56K Modem   ISDN (64 Kb)   ISDN (128 Kb)   Higher-speed Access  LD5655.V856_1977.K695.pdf 3.50 Mb 00:16:12 00:08:20 00:07:17 00:03:38 00:00:18 next to an author's name indicates that all files or directories associated with their ETD are accessible from the Virginia Tech campus network only.

If you have questions or technical problems, please Contact DLA.