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 Citations (Scopus)

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

Fingerprint

carbon 13
Anions
Negative ions
Carbon
Gases
Ions
chemistry
vapor phases
anions
Molecules
molecules
Cyclization
ions
Oxygen
Sulfur
adducts
oxygen
sulfur
carbon
Pipe flow

Keywords

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

ASJC Scopus subject areas

  • Spectroscopy

Cite this

The gas phase ion/molecule chemistry of the carbon- 13 labeled ketenyl and methyl ketenyl anions with CS2, COS, and CO2. / Robinson, Marin S; Davico, Gustavo E.; Bierbaum, Veronica M.; DePuy, Charles H.

In: International Journal of Mass Spectrometry and Ion Processes, Vol. 137, No. C, 06.10.1994, p. 107-119.

Research output: Contribution to journalArticle

@article{eaea2ae51f5b43cd8009310e24988d1c,
title = "The gas phase ion/molecule chemistry of the carbon- 13 labeled ketenyl and methyl ketenyl anions with CS2, COS, and CO2",
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.",
keywords = "Carbon-13 labeling, Gas phase reactions, Ion/molecule chemistry, Ketenyl anions",
author = "Robinson, {Marin S} and Davico, {Gustavo E.} and Bierbaum, {Veronica M.} and DePuy, {Charles H.}",
year = "1994",
month = "10",
day = "6",
doi = "10.1016/0168-1176(94)04030-3",
language = "English (US)",
volume = "137",
pages = "107--119",
journal = "International Journal of Mass Spectrometry",
issn = "1387-3806",
publisher = "Elsevier",
number = "C",

}

TY - JOUR

T1 - The gas phase ion/molecule chemistry of the carbon- 13 labeled ketenyl and methyl ketenyl anions with CS2, COS, and CO2

AU - Robinson, Marin S

AU - Davico, Gustavo E.

AU - Bierbaum, Veronica M.

AU - DePuy, Charles H.

PY - 1994/10/6

Y1 - 1994/10/6

N2 - 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.

AB - 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.

KW - Carbon-13 labeling

KW - Gas phase reactions

KW - Ion/molecule chemistry

KW - Ketenyl anions

UR - http://www.scopus.com/inward/record.url?scp=0006702133&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0006702133&partnerID=8YFLogxK

U2 - 10.1016/0168-1176(94)04030-3

DO - 10.1016/0168-1176(94)04030-3

M3 - Article

VL - 137

SP - 107

EP - 119

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

SN - 1387-3806

IS - C

ER -