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Efficient methods for the preparation of bromine-containing exo-nido- and closo-ruthenacarborane clusters

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Abstract

An efficient method for the synthesis of bromine-containing exo-nido-clusters of a general formula exo-5,6,10-[Br(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-R2-nido-7,8-C2B9H6 (R = H, Me) was developed using the reactions of RuBr2(PPh3)3 with [K][7,8-R2-7,8-nido-C2B9H10]. Replacement of the phosphine ligands in the starting exo-nido-cluster (R = H) with the diphosphine ones afforded a series of diamagnetic (18-electron) closo-bromoruthenacarboranes, 3-Br-3,3-[κ2-Ph2P(CH2) n PPh2]-3-H-closo-3,1,2-RuC2B9H11 (n = 3−5). A mild thermal method of the halide ligands exchange (Cl → Br) upon heating of diamagnetic chlorine-containing complexes 3,3-[κ2-Ph2P(CH2) n PPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 3−5) with excess of CBr4 in benzene (70–80 °C) was suggested for the synthesis of paramagnetic (17-electron) bromine-containing ruthenacarboranes, 3-Br-3,3-[κ2-Ph2P(CH2) n PPh2]-closo-3,1,2-RuC2B9H11 (n = 3, 4) or 3-Br-3,3,8-[κ2-Ph2(CH2)5PPh]-μ-. Paramagnetic chlorine-containing clusters 3-Cl-3,3-[κ2-Ph2P(CH2) n PPh2]-closo-3,1,2-RuC2B9H11 (n = 2−4) were alternatively used as the starting compounds in the exchange reaction. Complexes with dppp and dppb (dppp is 1,3-bis(diphenylphosphino)propane, dppb is 1,4-bis(diphenylphosphino)butane) were used as examples to study the thermal reactions (toluene, 110 °C) leading in the presence of CBr4 to paramagnetic mono(P-o-phenylene)- and bis(P,P-o-phenylene)cycloboronated clusters, 3-Br-3,3,8-[κ2-Ph2(CH2) n PPh]-μ- and 3-Br-3,3,4,8-[κ2-Ph2(CH2) n P]-μ- (n = 3, 4). The compounds obtained were characterized by NMR spectroscopy (in the case of diamagnetic complexes), ESR spectroscopy and mass spectrometry (in the case of paramagnetic compounds). X-ray diffraction experiments were carried out for two cycloboronated paramagnetic complexes.

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References

  1. D. N. Cheredilin, F. M. Dolgushin, A. A. Korlyukov, I. A. Godovikov, R. Kadyrov, E. V. Balagurova, S. P. Solodovnikov, I. T. Chizhevsky, Inorg. Chem. Commun., 2005, 8, 614.

    Article  CAS  Google Scholar 

  2. D. N. Cheredilin, R. Kadyrov, F. M. Dolgushin, E. V. Balagurova, I. A. Godovikov, S. P. Solodovnikov, I. T. Chizhevsky, J. Organomet. Chem., 2006, 691, 3889.

    Article  Google Scholar 

  3. D. N. Cheredilin, E. V. Balagurova, I. A. Godovikov, S. P. Solodovnikov, I. T. Chizhevsky, Russ. Chem. Bull. (Int. Ed.), 2005, 54, 2535 [Izv. Akad. Nauk, Ser. Khim., 2005, 2455].

    Article  CAS  Google Scholar 

  4. D. N. Cheredilin, F. M. Dolgushin, I. D. Grishin, E. V. Kolyakina, A. S. Nikiforov, S. P. Solodovnikov, M. M. Il’in, V. A. Davankov, I. T. Chizhevsky, D. F. Grishin, Russ. Chem. Bull. (It. Ed.), 2006, 55, 1163 [Izv. Akad. Nauk, Ser. Khim., 2006, 1120].

    Article  CAS  Google Scholar 

  5. I. D. Grishin, D. I. D’yachihin, A. V. Piskunov, F. M. Dolgushin, A. F. Smol’ykov, M. M. Il’in, V. A. Davankov, I. T. Chizhevsky, D. F. Grishin, Inorg. Chem., 2011, 50, 7574.

    Article  CAS  Google Scholar 

  6. I. D. Grishin, D. I. D’yachihin, E. S. Turmina, F. M. Dolgushin, A. F. Smol’ykov, A. V. Piskunov, I. T. Chizhevsky, D. F. Grishin, J. Organomet. Chem., 2012, 721–722, 113.

    Google Scholar 

  7. E. V. Kolyakina, I. D. Grishin, D. N. Cheredilin, F. M. Dolgushin, I. T. Chizhevsky, D. F. Grishin, Russ. Chem. Bull. (Int. Ed.), 2006, 55, 89 [Izv. Akad. Nauk, Ser. Khim., 2006, 85].

    Article  CAS  Google Scholar 

  8. I. D. Grishin, E. V. Kolyakina, D. N. Cheredilin, I. T. Chizhevsky, D. F. Grishin, Polymer Sci., Ser. A (Engl. Transl.), 2007, 49, 1079 [Vysokomolekulyar. Soedin. Ser. A, 2007, 49, 1766].

    Article  Google Scholar 

  9. I. D. Grishin, I. T. Chizhevsky, D. F. Grishin, Dokl. Chem. (Engl. Transl.), 2008, 423, 290 [Dokl. Akad. Nauk, 2008, 423, 340].

    CAS  Google Scholar 

  10. D. F. Grishin, I. D. Grishin, I. T. Chizhevsky, in Controlled/Living Radical Polymerization: Progress in ATRP, Ed. K. Matyaszewski, Am. Chem. Soc.: Symposium Series, 2009, 1023, 115.

    CAS  Google Scholar 

  11. I. D. Grishin, E. S. Turmina, D. I. D’yachihin, D. S. Vinogradov, A. V. Piskunov, A. F. Smol’ykov, F. M. Dolgushin, I. T. Chizhevsky, D. F. Grishin, Russ. Chem. Bull. (Int. Ed.), 2011, 60, 2375 [Izv. Akad. Nauk, Ser. Khim., 2011, 2328].

    Article  CAS  Google Scholar 

  12. I. D. Grishin, E. S. Turmina, I. T. Chizhevsky, D. F. Grishin, Polymer Sci., Ser. B (Engl. Transl.), 2012, 54, 383 [Vysokomolekulyar. Soedin. Ser. B, 2012, 54, 1304].

    Article  CAS  Google Scholar 

  13. I. D. Grishin, E. S. Turmina, D. I. D’yachihin, I. T. Chizhevsky, D. F. Grishin, Polymer Sci., Ser. B (Engl. Transl.), 2014, 56, 1 [Vysokomolekulyar. Soedin. Ser. B, 2014, 56, 3].

    Article  CAS  Google Scholar 

  14. Y. Kotani, M. Kamigaito, M. Sawamoto, Macromolecules, 1998, 31, 5582.

    Article  CAS  Google Scholar 

  15. M. Senoo, Y. Kotani, M. Kamigaito, M. Sawamoto, Macromolecules, 1999, 32, 8005.

    Article  CAS  Google Scholar 

  16. Y. Watanabe, T. Ando, M. Kamigaito, M. Sawamoto, Macromolecules, 2001, 34, 4370.

    Article  CAS  Google Scholar 

  17. S. V. Timofeev, I. A. Lobanova, P. V. Petrovskii, Z. A. Starikova, V. I. Bregadze, Russ. Chem. Bull. (Int. Ed.), 2001, 50, 2245 [Izv. Akad. Nauk, Ser. Khim., 2001, 2143].

    Article  CAS  Google Scholar 

  18. J. J. Levison, S. D. Robinson, J. Chem. Soc. A, Inorg. Phys. Theor., 1970, 2947.

    Google Scholar 

  19. P. R. Hoffman, K. G. Caulton, J. Am. Chem. Soc., 1975, 97, 4221.

    Article  CAS  Google Scholar 

  20. I. T. Chizhevsky, I. A. Lobanova, V. I. Bregadze, P. V. Petrovskii, V. A. Antonovich, A. V. Polyakov, A. I. Yanovsky, Yu. T. Struchkov, Mendeleev Commun., 1991, 47.

    Google Scholar 

  21. G. N. Kolomnikova, P. V. Petrovskii, P. V. Sorokin, F. M. Dolgushin, A. I. Yanovsky, I. T. Chizhevsky, Russ. Chem. Bull. (Int. Ed.), 2001, 50, 706 [Izv. Akad. Nauk, Ser. Khim., 2001, 677].

    Article  CAS  Google Scholar 

  22. I. V. Pisareva, F. M. Dolgushin, O. L. Tok, V. E. Konoplev, K. Yu. Suponitsky, A. I. Yanovsky, I. T. Chizhevsky, Organometallics, 2001, 20, 4216.

    Article  CAS  Google Scholar 

  23. J. Emsley, The Elements, Clarendon Press, Oxford, 1991.

    Google Scholar 

  24. K. Baše, A. Petr’ina, B. Štíbr, G. A. Kukina, I. A. Zakharova, Proc. 8th Conf. Coord. Chem. (Czechoslovakia), 1980, p. 17; Chem. Abstr., 1981, 95, 23933g.

    Google Scholar 

  25. J. E. Crook, N. N. Greenwood, J. D. Kennedy, W. S. McDonald, J. Chem. Soc., Chem. Commun., 1982, 383.

    Google Scholar 

  26. A. Weissberger, E. Proskauer, J. Riddick, E. Toops, Organic Solvents, Intersci. Publ., New York, 1955.

    Google Scholar 

  27. APEX II Software Package, Bruker AXS Inc., 5465 East Cheryl Parkway, Madison (WI), 5317, 2005.

    Google Scholar 

  28. G. M. Sheldrick, Acta Crystallogr., Sect. A, 2008, 64, 112.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    D. I. D’yachihin, I. A. Godovikov, A. Yu. Kostukovich, A. F. Smol’yakov, F. M. Dolgushin & I. T. Chizhevsky

  2. N. I. Lobachevsky Nizhny Novgorod State University, 23 prosp. Gagarina, 603950, Nizhny Novgorod, Russian Federation

    I. D. Grishin, A. V. Piskunov & D. F. Grishin

  3. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhny Novgorod, Russian Federation

    A. V. Piskunov

Authors
  1. D. I. D’yachihin
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  2. I. D. Grishin
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  3. A. V. Piskunov
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  4. I. A. Godovikov
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  5. A. Yu. Kostukovich
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  6. A. F. Smol’yakov
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  7. F. M. Dolgushin
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  8. I. T. Chizhevsky
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  9. D. F. Grishin
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Correspondence to I. T. Chizhevsky or D. F. Grishin.

Additional information

Dedicated to Academician of the Russian Academy of Sciences Yu. N. Bubnov on the occasion of his 80th birthday and to the 60th anniversary of A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2325–2333, October, 2014.

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D’yachihin, D.I., Grishin, I.D., Piskunov, A.V. et al. Efficient methods for the preparation of bromine-containing exo-nido- and closo-ruthenacarborane clusters. Russ Chem Bull 63, 2325–2333 (2014). https://doi.org/10.1007/s11172-014-0742-0

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  • DOI: https://doi.org/10.1007/s11172-014-0742-0

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