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Group and Site Selective σ-Bond Metathesis Reactions of CH_3ScCH_2CH_3^+ with [2,2-D_2]Propane, [1,1,1,4,4,4-D_6]-n-Butane, [2-D]-Isobutane, and n-Pentane

Crellin, Kevin C. and Geribaldi, Serge and Widmer, M. and Beauchamp, J. L. (1995) Group and Site Selective σ-Bond Metathesis Reactions of CH_3ScCH_2CH_3^+ with [2,2-D_2]Propane, [1,1,1,4,4,4-D_6]-n-Butane, [2-D]-Isobutane, and n-Pentane. Organometallics, 14 (9). pp. 4366-4373. ISSN 0276-7333. doi:10.1021/om00009a046.

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Fourier transform ion cyclotron resonance mass spectrometry has been used to examine the reactions of CH_3ScCH_2CH_3^+ with [D_4]methane, ethane, [2,2-D_2]propane, [1,1,1,4,4,4-D_6]-n-butane, [2-D]isobutane, n-pentane, and [D_12]-n-pentane. CH_3ScCH_2CH_3^+ is not observed to react with methane or ethane, but for propane, n-butane, isobutane, and n-pentane σ-bond metathesis with ethane elimination is the initial and dominant reaction observed, with further dehydrogenation of the resulting products occurring as additional reaction channels. For propane, n-butane, and isobutane, no methane elimination is observed. For n-pentane, methane elimination is a minor reaction channel. For propane, n-butane, and isobutane, the initial σ-bond metathesis involves predominantly the primary C-H bonds of the hydrocarbon. These processes are facile at room temperature and occur with little or no activation energy. Measured total bimolecular rate constants with [2,2-D_2]propane, [1,1,1,4,4,4-D_6]-n-butane [2-D]isobutane, and n-pentane are 0.87 x x 10^(-10), 0.98 x 10^(-10), 1.7 x and 6.4 x 10^(-10) cm^3 s^(-1) molecule^(-1), respectively. With the butanes and pentane a second intramolecular metathesis reaction follows the initial addition to yield a metallacycle product. In accordance with earlier theoretical predictions these metathesis reactions appear to proceed via an allowed four-center mechanism similar to that of a 2_σ + 2_σ cycloaddition. The higher reactivity of the metal-ethyl bond compared to the metal-methyl bond and the observed C-H bond specificity are also in agreement with theoretical predictions.

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Beauchamp, J. L.0000-0001-8839-4822
Alternate Title:Group and Site Selective .sigma.-Bond Metathesis Reactions of CH3ScCH2CH3+ with [2,2-D2]Propane, [1,1,1,4,4,4-D6]-n-Butane, [2-D]-Isobutane, and n-Pentane
Additional Information:© 1995 American Chemical Society. Received February 15, 1995. We wish to thank J. K. Perry and Professor W. A. Goddard III for their theoretical work on this system. This work was supported by the National Science Foundation under Grant CHE-9108318, by a grant from AMOCO, and by the Office of Naval Research.
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Office of Naval Research (ONR)UNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics9052
Issue or Number:9
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Official Citation:Group and Site Selective .sigma.-Bond Metathesis Reactions of CH3ScCH2CH3+ with [2,2-D2]Propane, [1,1,1,4,4,4-D6]-n-Butane, [2-D]-Isobutane, and n-Pentane Kevin C. Crellin, Serge Geribaldi, M. Widmer, and J. L. Beauchamp Organometallics 1995 14 (9), 4366-4373 DOI: 10.1021/om00009a046
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86508
Deposited By: George Porter
Deposited On:21 May 2018 20:59
Last Modified:15 Nov 2021 20:39

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