The gas phase ion/molecule chemistry of the carbon- 13 labeled ketenyl and methyl ketenyl anions with CS2, COS, and CO2

Marin S Robinson, Gustavo E. Davico, Veronica M. Bierbaum, Charles H. DePuy

Research output: Contribution to journalArticle

5 Scopus citations

Abstract

A flowing afterglow-selected ion flow tube apparatus was used to study the gas phase ion/molecule chemistry of carbon-13 labeled ketenyl anions (HCCO) with CS2, COS and CO2. In all cases, the ketenyl anion adds to the carbonyl carbon of the neutral; the resulting adduct undergoes subsequent cyclization and elimination, forming the thioketenyl anion (HCCS) in the reactions with CS2 and COS, and a degenerate anion in the reaction with CO2 in which the CO group of the ketenyl anion and that of CO2 are exchanged. In the reaction of the ketenyl anion with COS, both sulfur and oxygen participate in cyclization. After addition to carbon, sulfur undergoes cyclization approximately four times faster than oxygen, but all reactions eventually cyclize through oxygen before cleavage to product. An unexpectedly small reaction efficiency was observed in the reaction of the ketenyl anion with CS2. To explain this finding, we propose that energy randomization in the initially formed adduct is slow, thereby increasing the probability of decomposition. The reactions of carbon-13 labeled methyl ketenyl anions (CH3CCO) with CS2, COS, and CO2 were also studied and produce analogous results.

Original languageEnglish (US)
Pages (from-to)107-119
Number of pages13
JournalInternational Journal of Mass Spectrometry and Ion Processes
Volume137
Issue numberC
DOIs
StatePublished - Oct 6 1994
Externally publishedYes

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Keywords

  • Carbon-13 labeling
  • Gas phase reactions
  • Ion/molecule chemistry
  • Ketenyl anions

ASJC Scopus subject areas

  • Spectroscopy

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