TY - JOUR
T1 - Effect of lone-pair repulsion on the reactivity and selectivity of fluoroalkyl radicals
AU - El-Soueni, Amr
AU - Tedder, John M.
AU - Vertommen, Luc L.T.
AU - Walton, John C.
PY - 1977/12/1
Y1 - 1977/12/1
N2 - The relative rates of addition of trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, and nonafluoro-t-butyl radicals to ethylene and vinyl fluoride show that these radicals become increasingly selective as they become branched and there is a direct correlation between the logarithm of orientation of addition to vinyl fluoride of each radical and the pKa's of the corresponding perfluoroalkyl hydrides [CF3H, CF3CF 2H, (CF3)2CFH, and (CF3) 3CH]; these observations suggest that repulsion between the lone pair electrons on an α-fluorine atom and the unpaired electron on the trivalent carbon atom plays an important part in determining the reactivity of these radicals.
AB - The relative rates of addition of trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, and nonafluoro-t-butyl radicals to ethylene and vinyl fluoride show that these radicals become increasingly selective as they become branched and there is a direct correlation between the logarithm of orientation of addition to vinyl fluoride of each radical and the pKa's of the corresponding perfluoroalkyl hydrides [CF3H, CF3CF 2H, (CF3)2CFH, and (CF3) 3CH]; these observations suggest that repulsion between the lone pair electrons on an α-fluorine atom and the unpaired electron on the trivalent carbon atom plays an important part in determining the reactivity of these radicals.
UR - http://www.scopus.com/inward/record.url?scp=37049105399&partnerID=8YFLogxK
U2 - 10.1039/C39770000504
DO - 10.1039/C39770000504
M3 - Article
AN - SCOPUS:37049105399
SN - 0022-4936
SP - 504
EP - 505
JO - Journal of the Chemical Society, Chemical Communications
JF - Journal of the Chemical Society, Chemical Communications
IS - 14
ER -