Abstract
Deboration of 1-PhCH2-1,2-C2B10H11 by heating in ethanolic potassium hydroxide afforded Me4N+ [7-PhCH2-7,8-C2B9H11]− which was treated with excess halosuccinimide (NCS, NBS) in acetonitrile or with elemental iodine or bromine in methanol to obtain Me4N+ [7-PhCH2-9,11-X2-7,8-C2B9H9]− (X = Cl, Br, I). The reaction of 1-PhCH2-1,2-C2B10H11 with an equimolar amount of iodine gave a mixture of Me4N+·[7-PhCH2-11-I-7,8-C2B9H10]- and Me4N+[7-C6H5CH2-9-I-7,8-C2B9H10]− at a ratio 1:1.8 due to steric effect of the benzyl substituent. The 11B chemical shifts of each μ-H tautomer of Me4N+ [7-PhCH2-9,11-X2-7,8-C2B9H9]− (X = H, F, Cl, Br, I) were calculated at the DFT level of theory, and their contributions to the average 11B NMR spectrum and the corresponding tautomeric equilibrium constants were determined.
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Acknowledgments
The authors thank the Joint Chemical Service Center of the Novosibirsk Institute of Organic Chemistry (Siberian Branch, Russian Academy of Sciences) and head of the Laboratory of Physicochemical Methods Prof. A.V. Bara-novskii (Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus) for recording the spectra.
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Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 10, pp. 1540–1550.
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Rudakov, D.A., Genaev, A.M., Dikusar, E.A. et al. Halogenation and μH Tautomerism of 7-Benzyl-7,8-dicarba-nido-undecaborate(−1) Anion. Russ J Org Chem 55, 1495–1503 (2019). https://doi.org/10.1134/S1070428019100075
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DOI: https://doi.org/10.1134/S1070428019100075