Gas-Phase Synthesis and Reactions of Nitrogen- and Sulfur-Containing Anions

Article abstract of DOI:10.1021/j150651a031

The flowing afterglow and selected ion-flow tube techniques have been used to study the reactions of H2N^- with N2O, CO2, CS2, SO2, and OCS in the gas phase.Thermal energy rate coefficients and product branching ratios have been determined and are discussed in terms of detailed reaction mechanisms.With use of the SIFT-drift technique, the product distribution for the reaction of H2N^- with N2O was measured as a function of the center of mass kinetic energy in the range of thermal energy to ca. 15 kcal mol^1-.Qualitative studies were made of the reactions of HO^-, CH3O^-, and (CH3)2N^- with N2O, CO2, CS2, SO2, and OCS, and the reactions of a variety of other ions with OCS were also examined.These reactions provide efficient synthetic routes for the gas-phase preparation of a variety of interesting negative ions containing nitrogen and sulfur.The basicities and heats of formation of three of these anions, H2NS^-, NSO^-, and NCS^-, have been bracketed by proton-transfer reactions.The nucleophilicities of these three anions, as well as of H2N^-, HO^-, HO2^-, F^-, HS^-, CN^-, NCO^-, N3^-, Cl^-, and Br^- toward CH3I, have been measured.