The one-electron oxidation of [HCCOCC](-) to form neutral HCCOCC, and the subsequent rearrangement of HCCOCC to form HCCCCO: An experimental and computational study

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2006

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Fitzgerald, M.
Bowie, J.

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Rapid Communications in Mass Spectrometry, 2006; 20(4):577-582

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Mark Fitzgerald, John H. Bowie

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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.

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The definitive version may be found at www.wiley.com

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