The one-electron oxidation of [HCCOCC]- to form neutral HCCOCC, and the subsequent rearrangement of HCCOCC to form HCCCCO. An experimental and computational study.
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.
Fitzgerald
Mark
M
Department of Chemistry, The University of Adelaide, South Australia, Australia 5005.
Bowie
John H
JH