Gas-phase chemistry of vanadium oxide cluster cations. 1. Reactions with C2F6 and CH3CF3

Richard Curtis Bell, K. A. Zemski, A. W. Castleman

Research output: Contribution to journalArticle

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Abstract

The reactivities of mass-selected vanadium oxide cluster cations with fluorocarbons were studied by using a triple-quadrupole mass spectrometer coupled with a laser vaporization source. The vanadium oxide species V2O4-7+, V3O6-9+, V4O8-11+, V5O11-13+, V6O13-16+, and V7O16-18+ displayed unique reactivities with CH3-CF3 and C2F6. Among the reaction pathways observed were association, HF elimination, cracking of the carbon-carbon bond, and fluorine abstraction with oxygen transfer from the cluster to the neutral reactant molecule. Interestingly, the reactions differed for clusters within the same series and also from series to series. For example, the reaction of V2O4+ with CH3CF3 produces the HF-elimination product V2O4·HF+. However, the cluster V2O5+ reacts with CH3CF3 to produce the cracking product V2O5·CF3+ but also reacts to abstract 2 fluorine atoms with transfer of an oxygen atom to the neutral reactant molecule. The reaction of these 2 clusters with C2F6 generates only association products.

Original languageEnglish (US)
Pages (from-to)8293-8299
Number of pages7
JournalJournal of Physical Chemistry A
Volume102
Issue number43
StatePublished - Oct 22 1998

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Vanadium
Fluorine
vanadium oxides
Oxides
Cations
Carbon
Gases
Association reactions
chemistry
vapor phases
Oxygen
Fluorocarbons
cations
Atoms
Molecules
Mass spectrometers
Vaporization
fluorine
elimination
products

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "The reactivities of mass-selected vanadium oxide cluster cations with fluorocarbons were studied by using a triple-quadrupole mass spectrometer coupled with a laser vaporization source. The vanadium oxide species V2O4-7+, V3O6-9+, V4O8-11+, V5O11-13+, V6O13-16+, and V7O16-18+ displayed unique reactivities with CH3-CF3 and C2F6. Among the reaction pathways observed were association, HF elimination, cracking of the carbon-carbon bond, and fluorine abstraction with oxygen transfer from the cluster to the neutral reactant molecule. Interestingly, the reactions differed for clusters within the same series and also from series to series. For example, the reaction of V2O4+ with CH3CF3 produces the HF-elimination product V2O4·HF+. However, the cluster V2O5+ reacts with CH3CF3 to produce the cracking product V2O5·CF3+ but also reacts to abstract 2 fluorine atoms with transfer of an oxygen atom to the neutral reactant molecule. The reaction of these 2 clusters with C2F6 generates only association products.",
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Gas-phase chemistry of vanadium oxide cluster cations. 1. Reactions with C2F6 and CH3CF3. / Bell, Richard Curtis; Zemski, K. A.; Castleman, A. W.

In: Journal of Physical Chemistry A, Vol. 102, No. 43, 22.10.1998, p. 8293-8299.

Research output: Contribution to journalArticle

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