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Gas-phase studies of alkane oxidation by transition-metal oxides. Selective oxidation by CrO⁺

Kang, H. and Beauchamp, J. L. (1986) Gas-phase studies of alkane oxidation by transition-metal oxides. Selective oxidation by CrO⁺. Journal of the American Chemical Society, 108 (24). pp. 7502-7509. ISSN 0002-7863. doi:10.1021/ja00284a011.

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The gas-phase reactions of CrO⁺ with alkanes have been studied by using ion beam reactive scattering techniques. CrO⁺ undergoes facile reactions with alkanes larger than methane. CrO+ selectively oxidizes ethane to form ethanol. In addition to the possibility of alcohol formation, reactions with larger alkanes are more complex, yielding products in which dehydrogenation and loss of alkenes and alkanes occur. In reactions with cyclic alkanes, cyclopropane and cyclobutane yield products characteristic of C-C bond cleavage. In contrast, reactions with cyclopentane and cyclohexane mainly involve dehydrogenation and elimination of H₂O. A series of hydrogen abstraction reactions are examined to determine the bond dissociation energy D⁰(CrO⁺-H) = 89 ± 5 kcal mol⁻¹. This bond energy has implications for the reaction mechanisms of CrO⁺ with alkanes, leading to the suggestion of a multicenter reaction intermediate, in which alkyl C-H bonds add across the Cr⁺-O bond as an initial step. This is supported by an examination of the reactions of Cr⁺ with alcohols.

Item Type:Article
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Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 1986 American Chemical Society. Received February 24, 1986. We gratefully acknowledge the support of the National Science Foundation under Grant CHE-8407857. Graduate fellowship support by the Korean Government (H.K 1980-1984) is gratefully acknowledged.
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Government of KoreaUNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7319
Issue or Number:24
Record Number:CaltechAUTHORS:20200612-145542652
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Official Citation:Gas-phase studies of alkane oxidation by transition-metal oxides. Selective oxidation by CrO+. H. Kang and J. L. Beauchamp Journal of the American Chemical Society 1986 108 (24), 7502-7509 DOI: 10.1021/ja00284a011
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103897
Deposited By: George Porter
Deposited On:12 Jun 2020 22:43
Last Modified:16 Nov 2021 18:26

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