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Degenerate rearrangement of detectable 9,10-dimethyl-9-vinyl-phenanthrenium ion: 1,2-Shift of the vinyl group

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Abstract

Dynamic NMR study showed that 9,10-dimethyl-9-vinylphenanthrenium ion, generated under the conditions ensuring its “long life,” undergoes very fast (ΔG ≠ = 24.4 kJ/mol at −103°C) degenerate 1,2-shift of the vinyl group. According to the DFT quantum-chemical calculations, the process is one-step, and the low energy of formation of the activated complex is determined by effective participation of π electrons of the vinyl group in delocalization of the positive charge; no such delocalization is intrinsic to the initial ion.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    V. A. Bushmelev, A. M. Genaev & V. G. Shubin

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  1. V. A. Bushmelev
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  2. A. M. Genaev
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  3. V. G. Shubin
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Original Russian Text © V.A. Bushmelev, A.M. Genaev, V.G. Shubin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 1. pp. 107–113.

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Bushmelev, V.A., Genaev, A.M. & Shubin, V.G. Degenerate rearrangement of detectable 9,10-dimethyl-9-vinyl-phenanthrenium ion: 1,2-Shift of the vinyl group. Russ J Org Chem 42, 100–106 (2006). https://doi.org/10.1134/S1070428006010155

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  • DOI: https://doi.org/10.1134/S1070428006010155

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