A combined neutralization-reionization mass spectrometric and theoretical study of oxyallyl and other elusive [C₃,H₄,O] neutrals
Date
1998
Authors
Schalley, C.
Blanksby, S.
Harvey, J.
Schroder, D.
Zummack, W.
Bowie, J.
Schwarz, H.
Editors
Advisors
Journal Title
Journal ISSN
Volume Title
Type:
Journal article
Citation
European Journal of Organic Chemistry, 1998; 6(6):987-1009
Statement of Responsibility
Christoph A. Schalley, Stephen Blanksby, Jeremy N. Harvey, Detlef Schröder, Waltraud Zummack, John H. Bowie and Helmut Schwarz
Conference Name
Abstract
Five different anionic [C<inf>3′</inf>H<inf>4′</inf>O]<sup>•-</sup> 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 [C<inf>3′</inf>H<inf>4′</inf>O] <sup>•-/0/•+</sup> 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 <sup>1</sup>A<inf>1</inf> oxyallyl undergoes ring closure to cyclopropanone, and (v) triplet <sup>3</sup>B<inf>2</inf> oxyallyl may have a lifetime sufficient to survive a NR experiment.