DISSOCIATIVE ELECTRON-CAPTURE OF SULFONES AND SULFONATES - MATRIX-ISOLATION ESR STUDY

It is postulated that high sensitivity of poly(olefin sulfones) to electron beam irradiation results from a dissociative electron capture process: RSO2R + e- --> RSO2- + R.. Dialkyl sulfones RSO2R and alkyl alkanesulfonates ROSO2R were trapped in argon matrices together with Na atoms, and electron transfer between them was induced by mild radiation (lambda > 580 nm). ESR examination of the matrices revealed that all of the sulfones and sulfonates examined (dimethyl sulfone, diethyl sulfone, tetramethylene sulfone, ethyl methanesulfonate, and ethyl trifluoromethanesulfonate) readily captured an electron and dissociated to yield anions RSO2- or RSO3- and alkyl radicals R.. Cyclic tetramethylene sulfone, on capture of an electron, underwent a ring-opening process, yielding SO2-CH2CH2CH2CH2.. Ethyl and methyl radicals were generated with equal probability from ethyl methanesulfonate, but only the ethyl radical was generated in the case of ethyl trifluoromethanesulfonate.