title: Survey of the reactivity of O(2)(a (1)Delta(g)) with negative ions.
abstract: The reactivity of O(2)(a (1)Delta(g)) was studied with a series of anions, including (-)CH(2)CN, (-)CH(2)NO(2), (-)CH(2)C(O)H, CH(3)C(O)CH(2)(-), C(2)H(5)O(-), (CH(3))(2)CHO(-), CF(3)CH(2)O(-), CF(3)(-), HC(2)(-), HCCO(-), HC(O)O(-), CH(3)C(O)O(-), CH(3)OC(O)CH(2)(-), and HS(-). Reaction rate constants and product ion branching ratios were measured. All of the carbanions react through a common pathway to produce their major products. O(2)(a) adds across a bond at the site of the negative charge, resulting in the cleavage of this bond and the O=O bond. Oxyanions react through a hydride transfer to produce their major products. Proton transfer within these product ion-dipole complexes can occur, where the final branching ratios reflect the basicity of the resulting anions. Several of these anions (CF(3)(-), HC(2)(-), CH(3)OC(O)CH(2)(-)) were also found to undergo several sequential reactions within a single encounter. These three basic types of mechanisms are supported by calculations; a potential energy diagram for each type of reaction has been calculated. Additionally, six of these reactions had been qualitatively studied before; our results are in agreement with previous data.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
authors.forename: Nicole
authors.initials: N
authors.lastname: Eyet
authors.forename: Anthony
authors.initials: A
authors.lastname: Midey
authors.forename: Veronica M
authors.initials: VM
authors.lastname: Bierbaum
authors.forename: A A
authors.initials: AA
authors.lastname: Viggiano
mesh_terms: D000838:Anions / Q000737:chemistry; D003198:Computer Simulation; D008956:Models, Chemical; D010100:Oxygen / Q000737:chemistry*
chemical_list: D000838:Anions; D010100:Oxygen