By G. Leroy, D. Peeters, M. Sana, C. Wilante (auth.), Heinz G. Viehe, Zdenek Janousek, Robert Merényi (eds.)
`This e-book as a best point clinical kaleidoscope is usually recommended to all natural chemists and similar researchers who desire to understand and observe the result of the fashionable radical chemistry. a person who want to perform the intriguing extra improvement of this zone may still learn this booklet from hide to cover.'
Reaction Kinetics and Catalysis Letters, Vol. 34, No. 2, 1987
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Sample text
To illustrate this remark we shall successively consider the rotational barriers about the C-N bonds in aminoalkyl radicals and the barriers to internal rotation in I, I-substituted allyl radicals. These data are collected in table XIV and XV respectively. The stabilization energies of the corresponding species and those of the radicals which most resemble the moieties containing the unpaired electron in the transition structures are also given in the same tables. Table XIV. 6 a b In kcal mol -I Values corresponding to R:::COOH Table XV.
20 radical (R CH2) is the heat of reaction of the following isodesmic process : "IT We may write : ~Hoo = BDE(C-H) CH BDE(C - H) R CH 4 "IT 2 [ 17] This approach has been generalized to any type of radicals and it is the reason why the R-H bond dissociation energies have been widely used to estimate the unpaired electron delocalization energies of these species. The definitions gf Benson and Rodgers et al. only differ from the previous one by the choice of the isodesmic reaction, CH4 being replaced in this process by R CH3 or C2H6 respectively.
D. Beckhaus and C. Ruchardt, to appear in the NATO ASI Series on Substituent Effects in Radical Chemistry, Reidel, Dordrecht (1986). (thi;-VOiume) 90. D. C. U. Ingold, J. Am. Chem. , 97,6151 (1975). 91. W~K. Wilmarth and N. Schwartz, J. Am. Chem. Soc~, ZZ, 4543 (1955). 92. K. Schlosser and S. Steenken, J. Am. Chem. , 105, 1504 (1983). 93. C. -D. Beckhaus in Synthetic OrganI~=Chemistry, Springer Verlag, Berlin, Heidelberg, New York, Tokyo, pp. 1-23 (1986) • 94. M. H. Kaiser, H. -D. Beckhaus and C.