FORMATION AND CHARACTERIZATION OF THE SULFUR-CONTAINING DISTONIC RADICAL-ANION, CH(2)-S-(C)OVER-BAR-H-CN, IN THE GAS-PHASE

The reactions of the atomic oxygen radical anion O- with CH3-S-CH2-CN in the gas phase have been examined with Fourier transform ion cyclotron resonance in combination with tandem mass spectrometric experiments performed with a double-focusing quadrupole hybrid instrument. Deuterium labeling has revealed that the O- ion reacts with CH3-S-CH2-CN by proton abstraction from the methylene group as well as by competing 1,1- and 1,3-H2+ abstractions to afford isomeric radical anions. High kinetic energy (8 keV) collision-induced charge reversal experiments indicate that the 1,1-H2+-abstraction leads to a CH3-S-CBAR-CN carbene ion, whereas the 1,3-H2+ abstraction yields a novel sulfur-containing distonic radical anion, which is formulated as CH2-S-CBARH-CN.