title: The one-electron oxidation of [HCCOCC]- to form neutral HCCOCC, and the subsequent rearrangement of HCCOCC to form HCCCCO. An experimental and computational study.
abstract: The singlet anion [HCCOCC]- may be made in the source of a VG ZAB 2HF mass spectrometer by the reaction between F- (from SF6) and H-C[triple chemical bond]C-O-C[triple chemical bond]C-TMS. Vertical (Franck-Condon) one-electron oxidation of [HCCOCC]- in the first collision cell produces doublet neutral HCCOCC. A combination of experiment and molecular modelling [at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31 + G(d) level of theory] provides data which are consistent with some HCCOCC neutrals being stable for the duration of the neutralisation reionisation experiment, while others rearrange to form the decomposing doublet neutral HCCCCO.
authors.affiliation: Department of Chemistry, The University of Adelaide, South Australia, Australia 5005.
authors.forename: Mark
authors.initials: M
authors.lastname: Fitzgerald
authors.forename: John H
authors.initials: JH
authors.lastname: Bowie