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

研究成果: ジャーナルへの寄稿記事

62 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)3933-3943
ページ数11
ジャーナルOrganometallics
22
発行部数19
DOI
出版物ステータス出版済み - 9 15 2003

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Propane
Alkanes
butanes
Chain length
propane
alkanes
reactivity
Gases
vapor phases
Oxidation
oxidation
elimination
Butanes
Cyclotron resonance
Vanadium
Potential energy surfaces
Ethane
vanadium oxides
Deuterium
Dehydrogenation

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Alkane oxidation by VO2+ in the gas phase : A unique dependence of reactivity on the chain length. / Engeser, Marianne; Schlangen, Maria; Schröder, Detlef; Schwarz, Helmut; Yumura, Takashi; Yoshizawa, Kazunari.

:: Organometallics, 巻 22, 番号 19, 15.09.2003, p. 3933-3943.

研究成果: ジャーナルへの寄稿記事

Engeser, M, Schlangen, M, Schröder, D, Schwarz, H, Yumura, T & Yoshizawa, K 2003, 'Alkane oxidation by VO2+ in the gas phase: A unique dependence of reactivity on the chain length', Organometallics, 巻. 22, 番号 19, pp. 3933-3943. https://doi.org/10.1021/om030353h
Engeser, Marianne ; Schlangen, Maria ; Schröder, Detlef ; Schwarz, Helmut ; Yumura, Takashi ; Yoshizawa, Kazunari. / Alkane oxidation by VO2+ in the gas phase : A unique dependence of reactivity on the chain length. :: Organometallics. 2003 ; 巻 22, 番号 19. pp. 3933-3943.
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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.",
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