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https://hdl.handle.net/2440/17813
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Type: | Journal article |
Title: | The formation of neutral CCCO₂H and HCCCO₂ molecules from anionic precursors in the gas phase: a joint experimental and theoretical study |
Other Titles: | The formation of neutral CCCO(2)H and HCCCO(2) molecules from anionic precursors in the gas phase: a joint experimental and theoretical study |
Author: | Fitzgerald, M. Bowie, J. Schroder, D. Schwarz, H. |
Citation: | Rapid Communications in Mass Spectrometry, 2005; 19(24):3705-3712 |
Publisher: | John Wiley & Sons Ltd |
Issue Date: | 2005 |
ISSN: | 0951-4198 1097-0231 |
Statement of Responsibility: | Mark Fitzgerald, John H. Bowie, Detlef Schröder, Helmut Schwarz |
Abstract: | Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory indicate that the anions -CCCO2H and HCCCO2(-) are stable species in their singlet states. Upon collision-induced, vertical one-electron oxidation under neutralisation-reionisation (-NR+) conditions, they produce the neutral molecules CCCO2H and HCCCO2, respectively. Some of the CCCO2H neutrals should be stable for the duration of the neutralisation-reionisation experiment (10(-6) s), while others will dissociate to CCCO and OH (requires 125 kJ mol(-1)). In contrast, neutral HCCCO2 is expected to be much less stable, and dissociate to HCC and CO2 (37 kJ mol(-1)). Neither CCCO2H nor HCCCO2 is expected to interconvert, or to rearrange to other isomers. The anions -CCCO2H and HCCCO2(-) have been formed in the ion source of the mass spectrometer by the reactions between (CH3)3Si-C[triple bond]C-CO2H and F- and HC[triple bond]C-CO2Si(CH3)3 and F-, respectively. The -NR+ spectrum of -CCCO2H shows a recovery signal and also indicates that the lowest energy dissociation pathway of neutral CCCO2H corresponds to the loss of OH. The -NR+ spectrum of HCCCO2 displays little or no recovery signal, and the spectrum is dominated by the [CO2]+ ion. The experimental observations are in agreement with the predictions of the extensive theoretical studies. |
DOI: | 10.1002/rcm.2245 |
Published version: | http://dx.doi.org/10.1002/rcm.2245 |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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