The gas phase ion/molecule chemistry of four carbanions generated from vinylene carbonate and its methyl and dimethyl derivatives

Marin S Robinson, Fred W. Breitbeil

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, {A figure is presented} and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HCCO-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3CCO- and CH2CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HCCS- and CH3CCS-. The ions CH2CC(O)CH3 and CH2CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.

Original languageEnglish (US)
Pages (from-to)647-658
Number of pages12
JournalInternational Journal of Mass Spectrometry and Ion Processes
Volume117
Issue numberC
DOIs
StatePublished - Sep 1 1992
Externally publishedYes

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Carbonates
carbonates
Gases
Ions
chemistry
vapor phases
Derivatives
Anions
Molecules
Deuterium
Negative ions
Protons
molecules
Hydrogen
ions
anions
deuterium
Ion exchange
Atoms
protons

Keywords

  • carbanions
  • flowing afterglow
  • ion/molecule reactions
  • SIFT
  • vinylene carbonate

ASJC Scopus subject areas

  • Spectroscopy

Cite this

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title = "The gas phase ion/molecule chemistry of four carbanions generated from vinylene carbonate and its methyl and dimethyl derivatives",
abstract = "The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, {A figure is presented} and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HCCO-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3CCO- and CH2CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HCCS- and CH3CCS-. The ions CH2CC(O)CH3 and CH2CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.",
keywords = "carbanions, flowing afterglow, ion/molecule reactions, SIFT, vinylene carbonate",
author = "Robinson, {Marin S} and Breitbeil, {Fred W.}",
year = "1992",
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T1 - The gas phase ion/molecule chemistry of four carbanions generated from vinylene carbonate and its methyl and dimethyl derivatives

AU - Robinson, Marin S

AU - Breitbeil, Fred W.

PY - 1992/9/1

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N2 - The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, {A figure is presented} and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HCCO-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3CCO- and CH2CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HCCS- and CH3CCS-. The ions CH2CC(O)CH3 and CH2CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.

AB - The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, {A figure is presented} and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HCCO-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3CCO- and CH2CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HCCS- and CH3CCS-. The ions CH2CC(O)CH3 and CH2CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.

KW - carbanions

KW - flowing afterglow

KW - ion/molecule reactions

KW - SIFT

KW - vinylene carbonate

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