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Halogenation and μH Tautomerism of 7-Benzyl-7,8-dicarba-nido-undecaborate(−1) Anion

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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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References

  1. Hawthorne, M.F., Young, D.C., Garrett, P.M., Owen, D.A., Schwerin, S.G., Tebbe, F.N., and Wegner, P.A., J. Am. Chem. Soc., 1968, vol. 90, p. 862. https://doi.org/10.1021/ja01006a006

    Article  CAS  Google Scholar 

  2. Hermanek, S., Chem. Rev., 1992, vol. 92, p. 325. https://doi.org/10.1021/cr00010a007

    Article  CAS  Google Scholar 

  3. Hermanek, S., Inorg. Chim. Acta, 1999, vol. 289, p. 20. https://doi.org/10.1016/S0020-1693(99)00055-9

    Article  CAS  Google Scholar 

  4. Rudakov, D.A., Dikusar, E.A., and Zubreichuk, Z.P., Sintez i khimicheskie svoistva karboranov. Dikarbaun-dekaboraty, metallo- i metallacarborany, azometiny, slozhnye efiry, peroksidy, soli karborankarbonovykh kislot (Synthesis and Chemical Properties of Carboranes. Dicarbaundecaborates, Metallo- and Metalla-carboranes, Schiff Bases, Esters, Peroxides, and Carboranecarboxylic Acid Salts), Riga: LAP LAMBERT Academic, 2013.

    Google Scholar 

  5. Janousek, Z. and Kaszynski, P., Polyhedron, 1999, vol. 18, p. 3517. https://doi.org/10.1016/S0277-5387(99)00300-9

    Article  CAS  Google Scholar 

  6. Rudakov, D.A., Shirokii, V.L., Potkin, V.I., Dikusar, E.A., Bragin, V.I., Petrovskii, P.V., Sivaev, I.B., Bregadze, V.I., and Kisin, A.V., Russ. J. Electrochem., 2006, vol. 42, p. 280. https://doi.org/10.1134/S102319350603013X

    Article  CAS  Google Scholar 

  7. Winberg, K.J., Persson, M., Malmstrom, P.U., Sjoberg, S., and Tolmachev, V., Nucl. Med Biol., 2004, vol. 31, p. 425. https://doi.org/10.1016/j.nucmedbio.2003.11.007

    Article  CAS  Google Scholar 

  8. Gullon, T.J., MS Thesis, Hamilton: McMaster University, 2010.

    Google Scholar 

  9. Ghirmai, S., Malmquist, J., Lundquist, H., Tolmachev, V., and Sjoberg, S., J. Labelled Compd. Radiopharm., 2004, vol. 47, p. 557. https://doi.org/10.1002/jlcr.840

    Article  CAS  Google Scholar 

  10. Green, A.E.C., Parker, S.K., and Valliant, J.F., J. Organomet. Chem., 2009, vol. 694, p. 1736. https://doi.org/10.1016/j.jorganchem.2008.12.063

    Article  CAS  Google Scholar 

  11. El-Zaria, M.E., Janzen, N., Blacker, M., and Valliant, J.F., Chem. Eur. J., 2012, vol. 18, p. 11 071. https://doi.org/10.1002/chem.201200833

    Article  CAS  Google Scholar 

  12. El-Zaria, M.E., Genady, A.R., Janzen, N., Petlura, C.I., Vera, D.R.B., and Valliant, J.F., Dalton Trans., 2014, vol. 43, p. 4950. https://doi.org/10.1039/c3dt53189a

    Article  CAS  Google Scholar 

  13. Genady, A.R., Tan, J., El-Zaria, M.E., Zlitni, A., Janzen, N., and Valliant, J.F., J. Organomet. Chem., 2015, vol. 798, p. 278. https://doi.org/10.1016/j.jorganchem.2015.10.030

    Article  CAS  Google Scholar 

  14. Mizusawa, E.A., Thompson, M.R., and Hawthorne, M.F., Inorg. Chem., 1985, vol. 24, p. 1911. https://doi.org/10.1021/ic00206a043

    Article  CAS  Google Scholar 

  15. Kazakov, G.S., Sivaev, I.B., Suponitsky, K.Yu., Kirilin, A.D., Bregadze, V.I., and Welch, A.J., J. Organomet. Chem., 2016, vol. 805, p. 1. https://doi.org/10.1016/j.jorganchem.2016.01.009

    Article  CAS  Google Scholar 

  16. Olsen, F.P. and Hawthorne, M.F., Inorg. Chem., 1965, vol. 4, p. 1839. https://doi.org/10.1021/ic50034a047

    Article  CAS  Google Scholar 

  17. Semin, G.K., Zakharkin, L.I., Kuznetsov, S.I., Zhigareva, G.G., and Bryukhova, E.V., Russ. J. Gen. Chem., 1998, vol. 68, p. 919.

    CAS  Google Scholar 

  18. Shirokii, V.L., Rudakov, D.A., Bazhanov, A.V., Zalesskaya, E.G., Potkin, V.I., Maier, N.A., Timofeev, S.V., Petrovskii, P.V., and Bregadze, V.I., Russ. J. Electrochem., 2004, vol. 40, p. 212. https://doi.org/10.1023/B:RUEL.0000016338.23698.61

    Article  CAS  Google Scholar 

  19. Zakharkin, L.I., Kobak, V.V., Kovredov, A.I., and Antonovich, V.A., Bull. Acad. Sci. USSR, Div. Chem. Sci., 1979, vol. 28, no. 9, p. 1953. https://doi.org/10.1007/BF00952487

    Article  Google Scholar 

  20. Zakharkin, L.I., Zhigareva, G.G., and Antonovich, V.A., Zh. Obshch. Khim., 1980, vol. 50, p. 1026.

    CAS  Google Scholar 

  21. Santos, E.C., Pinkerton, A.B., Kinkead, S.A., Hurlburt, P.K., Jasper, S.A., Sellers, C.W., Huffman, J.C., and Todd, L.J., Polyhedron, 2000, vol. 19, p. 1777. https://doi.org/10.1016/S0277-5387(00)00461-7

    Article  CAS  Google Scholar 

  22. Grimes, R.N., Carboranes, New York: Academic, 2016, 3rd ed.

    Google Scholar 

  23. Boron Science: New Technologies and Applications, Hosmane, N.S., Ed., Boca Raton: CRC Press, 2012.

  24. Wiesboeck, R.A. and Hawthorne, M.F., J. Am. Chem. Soc., 1964, vol. 86, p. 1642. https://doi.org/10.1021/ja01062a042

    Article  CAS  Google Scholar 

  25. Rudakov, D.A., Shirokii, V.L., Potkin, V.I., Maier, N.A., Bragin, V.I., Petrovskii, P.V., Sivaev, I.B., Bregadze, V.I., and Kisin, A.V., Russ. Chem. Bull., Int. Ed., 2005, vol. 54, p. 1599. https://doi.org/10.1007/s11172-006-0009-5

    Article  CAS  Google Scholar 

  26. Lebedev, V.N., Balagurova, E.V., and Zakharkin, L.I., Russ. Chem. Bull., 1995, vol. 44, p. 1102. https://doi.org/10.1007/BF00707062

    Article  Google Scholar 

  27. Rudakov, D.A., Potkin, V.I., Ryabtsev, A.N., and Sivaev, I.B., J. Appl. Spectrosc., 2006, vol. 73, p. 616. https://doi.org/10.1007/s10812-006-0128-7

    Article  CAS  Google Scholar 

  28. Machacek, J., Buhl, M., Fanfrlik, J., and Hnyk, D., J. Phys. Chem. A, 2017, vol. 121, p. 9631. https://doi.org/10.1021/acs.jpca.7b09831

    Article  CAS  Google Scholar 

  29. Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865. https://doi.org/10.1103/PhysRevLett.77.3865

    Article  CAS  Google Scholar 

  30. Laikov, D.N., Chem. Phys. Lett., 1997, vol. 281, p. 151. https://doi.org/10.1016/S0009-2614(97)01206-2

    Article  CAS  Google Scholar 

  31. Laikov, D.N. and Ustynyuk, Yu.A., Russ. Chem. Bull., Int. Ed., 2005, vol. 54, p. 820. https://doi.org/10.1007/s11172-005-0329-x

    Article  CAS  Google Scholar 

  32. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N., Nguyen, K.A., Su, S.J., Windus, T.L., Dupuis, M., and Montgomery, J.A., Jr., J. Comput. Chem., 1993, vol. 14, p. 1347. https://doi.org/10.1002/jcc.540141112

    Article  CAS  Google Scholar 

Download references

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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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    D. A. Rudakov & A. M. Genaev

  2. Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus

    E. A. Dikusar, T. D. Zvereva, Z. P. Zubreichuk & V. I. Potkin

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  1. D. A. Rudakov
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  2. A. M. Genaev
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  3. E. A. Dikusar
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  5. Z. P. Zubreichuk
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  6. V. I. Potkin
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Correspondence to D. A. Rudakov.

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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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