A combined neutralization-reionization mass spectrometric and theoretical study of oxyallyl and other elusive [C3,H4,O] neutrals

Schalley, C. A., Blanksby, Stephen J., Harvey, J. N., Schröder, D., Zummack, W., Bowie, J. H., & Schwarz, H. (1998) A combined neutralization-reionization mass spectrometric and theoretical study of oxyallyl and other elusive [C3,H4,O] neutrals. European Journal of Organic Chemistry, pp. 987-1009.

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Five different anionic [C3′H4′O]•- isomers, i.e. the radical anions of acrolein, acetyl carbene, formyl methyl carbene, methoxy vinylidene, and oxyallyl are generated in an ion beam mass spectrometer and subjected to neutralization-reionization (NR) mass spectrometric experiments including neutral and ion decomposition difference (NIDD) mass spectrometry; the latter allows for the examination of the neutrals' unimolecular reactivity. Further, the anionic, the singlet and triplet neutral, and the cationic [C3′H4′O] •-/0/•+ potentialenergy surfaces are calculated at the B3LYP/6-311++G(d,p) level of theory. For some species, notably the singlet state of oxyallyl, the theoretical treatment is complemented by G2, CASSCF, and MR-CI calculations. Theory and experiment are in good agreement in that at the neutral stage (i) acrolein does not react within the μsec timescale, (ii) acetyl and formyl methyl carbenes isomerize to methyl ketene, (iii) methoxy vinylidene rearranges to methoxy acetylene, (iv) singlet 1A1 oxyallyl undergoes ring closure to cyclopropanone, and (v) triplet 3B2 oxyallyl may have a lifetime sufficient to survive a NR experiment.

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ID Code: 71277
Item Type: Journal Article
Refereed: Yes
Keywords: Density functional theory, Ketocarbenes, Methoxy vinylidene, Neutralization-reionization mass spectrometry, Oxyallyl
DOI: 10.1002/(SICI)1099-0690(199806)1998:6<987::AID-EJOC987>3.0.CO;2-G
ISSN: 1099-0690 (online) 1434-193X (print)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 1998 WILEY-VCHVerlag GmbH, D-69451Weinheim
Deposited On: 09 May 2014 00:55
Last Modified: 09 May 2014 00:55

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