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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[BOND]C[TRIPLE BOND]C[BOND]O[BOND]C[TRIPLE BOND]C[BOND]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. Copyright © 2006 John Wiley & Sons, Ltd.