title: Kinetics of self-decomposition and hydrogen atom transfer reactions of substituted phthalimide N-oxyl radicals in acetic acid.
abstract: Kinetic data have been obtained for three distinct types of reactions of phthalimide N-oxyl radicals (PINO(.)) and N-hydroxyphthalimide (NHPI) derivatives. The first is the self-decomposition of PINO(.) which was found to follow second-order kinetics. In the self-decomposition of 4-methyl-N-hydroxyphthalimide (4-Me-NHPI), H-atom abstraction competes with self-decomposition in the presence of excess 4-Me-NHPI. The second set of reactions studied is hydrogen atom transfer from NHPI to PINO(.), e.g., PINO(.) + 4-Me-NHPI <=> NHPI + 4-Me-PINO(.). The substantial KIE, k(H)/k(D) = 11 for both forward and reverse reactions, supports the assignment of H-atom transfer rather than stepwise electron-proton transfer. These data were correlated with the Marcus cross relation for hydrogen-atom transfer, and good agreement between the experimental and the calculated rate constants was obtained. The third reaction studied is hydrogen abstraction by PINO(.) from p-xylene and toluene. The reaction becomes regularly slower as the ring substituent on PINO(.) is more electron donating. Analysis by the Hammett equation gave rho = 1.1 and 1.8 for the reactions of PINO(.) with p-xylene and toluene, respectively.
authors.affiliation: Ames Laboratory and Department of Chemistry, Iowa State University of Science and Technology, Ames, Iowa 50011, USA.
authors.forename: Yang
authors.initials: Y
authors.lastname: Cai
authors.forename: Nobuyoshi
authors.initials: N
authors.lastname: Koshino
authors.forename: Basudeb
authors.initials: B
authors.lastname: Saha
authors.forename: James H
authors.initials: JH
authors.lastname: Espenson