Alkane oxidation by VO2+ in the gas phase: A unique dependence of reactivity on the chain length

Marianne Engeser, Maria Schlangen, Detlef Schröder, Helmut Schwarz, Takashi Yumura, Kazunari Yoshizawa

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64 Citations (Scopus)

Abstract

The oxidation of small alkanes by the vanadium oxide cation VO2+ in the gas phase has been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FTICR-MS). Sophisticated mass spectrometric experiments in conjunction with investigation of deuterium-labeled substances are used to elucidate the mechanistic details of the reactions. In marked contrast to oxidative dehydrogenation followed by elimination of ethene in the reaction of VO2+ with ethane, the corresponding reaction with propane mainly affords elimination of dihydrogen concomitant with an ionic product assigned to the allyl complex (η3-C3H5)V(O)-(OH)+. In the case of n-butane/VO2+, a combined loss of H2 and H2O provides yet another product channel. Branching ratios, reaction rates, and some mechanistic aspects of the oxidation of propane, n-butane, and isobutane by VO2+ are reported. The experiments are complemented by a computational study of the potential energy surface of propane/VO2+ by means of density functional theory.

Original languageEnglish
Pages (from-to)3933-3943
Number of pages11
JournalOrganometallics
Volume22
Issue number19
DOIs
Publication statusPublished - Sep 15 2003

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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