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A Combined Neutralization‐Reionization Mass Spectrometric and Theoretical Study of Oxyallyl and Other Elusive [C 3 , H 4 , O] Neutrals
Author(s) -
Schalley Christoph A.,
Blanksby Stephen,
Harvey Jeremy N.,
Schröder Detlef,
Zummack Waltraud,
Bowie John H.,
Schwarz Helmut
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199806)1998:6<987::aid-ejoc987>3.0.co;2-g
Subject(s) - chemistry , carbene , singlet state , photochemistry , acrolein , cumulene , reactivity (psychology) , radical , mass spectrometry , ion , medicinal chemistry , computational chemistry , organic chemistry , excited state , catalysis , atomic physics , molecule , pathology , chromatography , medicine , physics , alternative medicine
Five different anionic [C 3 , H 4 , 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 [C 3 , H 4 , O] ·−/0/·+ potential‐energy 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 1 A 1 oxyallyl undergoes ring closure to cyclopropanone, and (v) triplet 3 B 2 oxyallyl may have a lifetime sufficient to survive a NR experiment.