Methods of synthesis of metallaboranes with polyhedral cage [MB₉H₉], M=Ni, Pd

A new method of synthesis of polyhedral metallaboranes [ MB₉ H₉ ] ( M = Ni , Pd ) with an apical metal atom was suggested . The method consists in a reaction between ((C₆H₅)₄P)₂[B₉H₉] and different metal complexes of Ni(I), Ni(II) and Pd(II) both in organic solutions and in solid state with mechanical activation. The obtained metallaboranes were described with IR, NMR spectral data and elemental analysis.

boron hydrides, metallaboranes, nickel, palladium, nickelaboranes, palladaboranes, closoborates.

1. Safronov A.V., Shlyakhtina N.I., Hawthorne M.F. New approach to the synthesis of 3-alkyl-1,2-dicarba-closo-dodecaboranes: Reaction of alkyldichloroboranes with thallium dicarbollide // Organometallics. 2012. V. 31. № 7. P. 2764–2769.

2. Du S., Kautz J.A., McGrath T.D., Stone F.G.A. Synthesis and reactivity of the monocarbon molybdenacarborane anion [1,2-μ-NHBut-2,2,2-(CO)3-closo-2,1-MoCB10H10]– // Inorg. Chem. 2001. V. 40. № 26. P. 6563–6571.

3. Franken A., McGrath T.D., Stone F.G.A. 10-Vertex manganese−dicarbollide complexes from a monocarbon precursor. Synthesis and cluster vertex functionalization of [1-OH-2,2,2-(CO)3-closo-2,1,10-MnC2B7H8]− // Organometallics. 2009. V. 28. № 1. P. 225–235.

4. Franken A., McGrath T.D., Stone F.G.A. Synthesis and reactivity of the 9- and 10-vertex iron−monocarborane anions [7,7,7-(CO)3-closo-7,1-FeCB7H8]– and [6,6,6,10,10,10-(CO)6-closo-6,10,1-Fe2CB7H8]– // Organometallics. 2005. V. 24. № 21. P. 5157–5166.

5. Chizhevsky I.T., Petrovskii P.V., Sorokin P.V., Bregadze V.I., Dolgushin F.M., Yanovsky A.I., Struchkov Yu.T., Demonceau A., Noels A.F. Synthesis, characterization, and molecular structure of the first closo-hydrido complexes of osmium with carborane ligands: closo-3,3-(PPh3)2-3-H-3-Cl-3,1,2-OsC2B9H11 and closo-3,3-(PPh3)2-3,3-H2-1,2-Me2-3,1,2-OsC2B9H9 // Organometallics. 1996. V. 15. № 11. P. 2619–2623.

6. Lei P., McGrath T.D., Stone F.G.A. Oxidation of the bis-molybdenum(0) trianion [1,3,6-{Mo(CO)3}-3,6-(μ-H)2-1,1,1-(CO)3-2-Ph-closo-1,2-MoCB9H7]3–: Metal and boron vertex substitution and cluster expansion // Organometallics. 2006. V. 25. № 8. P. 2011–2017.

7. Franken A., McGrath T.D., Stone F.G.A. A 10-vertex iron−dicarbollide system formed by insertion of {Fe(CO)4} into 8-vertex [closo-1-CB7H8]−: Synthesis and reactivity studies // Organometallics. 2008. V. 27. № 5. P. 908–917.

8. Leyden R.N., Sullivan B.P., Baker R.T., Hawthorne M.F. Synthesis of closo- and nido-metalloboranes from metallocenes // J. Am. Chem. Soc. 1978. V. 100. № 12. P. 3758–3765.

9. Jasper S.A., Huffman J. C., Todd L.J. Synthesis of a metallaborane complex containing Pd(III) and the first doubly charge compensated ollide ion. X-ray crystal structure of 1,4-Br2-1,2,5-(PMe2Ph)3-closo-1-PdB11H8 // Inorg. Chem. 1998. V. 37. № 23 P. 6060–6064.

10. Органикум: в 2-х т.: пер. с нем. – М.: Мир, 1992. Т. 1. 487 с. Т. 2. 474 с.

11. Быков А.Ю., Разгоняева Г.А., Мальцева Н.Н., Жижин К.Ю., Кузнецов Н.Т. Новый метод синтеза аниона B3H8– // Журн. неорган. химии. 2012. Т. 57. № 4. С. 531–534.

12. Klanberg F., Muetterties E.L. Chemistry of boranes. XXVII. New polyhedral borane anions, B9H92– and B11H112– // Inorg. Chem. 1966. V. 5. № 11. P. 1955–1960.

13. Lipscomb W.N. Framework rearrangement in boranes and carboranes // Science. 1966. V. 153. № 373. P. 373–378.

14. Leites L.A. Vibrational spectroscopy of carboranes and parent boranes and its capabilities in carborane chemistry // Chem. Rev. 1992. V. 92. P. 279–323.

15. Zhizhin K.Yu., Mal'tseva N.N., Bykov A.Yu., Kuznetsov N.T. Modern aspects of the chemistry of complex boron and aluminum hydrides // Rus. J. Inorg. Chem. 2010. V. 55. № 14. P. 2128–2147.