Metal-Promoted Exopolyhedral Substitution of Terminal Hydrogen Atoms in the Closo-Decaborate Anion [B10H10]2– in the Presence of Copper(II): Formation of the Substituted Derivative [2-B10H9OH]2–

Abstract

Copper(II) complexation of the [B10H10]2– anion has been studied in the presence of 2,2′-bipyridyl (bipy) in organic solvents. The reaction between CuCl, bipy, and (Et3NH)[Ag[B10H10]] in DMF leads to copper(II) complex [Cu2(bipy)4(µ-CO3)][B10H10]·2DMF·H2O. The copper complexation reaction has been performed under the redox conditions Cu(I)  → Cu(II) in the presence of silver(I) compounds. When [Cu2(bipy)4(µ-CO3)][B10H10]·2DMF·H2O has been heated in DMSO, the monosubstituted derivative [2-B10H9OH]2– has been isolated as complex [Cu2(bipy)4(µ-CO3)][2-B10H10O0.17]·2DMSO·H2O consisting of the [B10H10]2– anion and its monosubstituted derivative [2-B10H9OH]2– cocrystallized in the 0.83:0.17 ratio. The metal-promoted process of exopolyhedral substitution of terminal hydrogen atoms in the [B10H10] anion in the presence of Cu(II) compounds has been discussed. Complexes synthesized have been studied by elemental analysis, IR, 1H and 11B NMR spectroscopy; the X-ray diffraction studies were performed for [Cu2(bipy)4(µ-CO3)][B10H10]·2DMF·H2O and [Cu2(bipy)4(µ-CO3)][2-B10H10O0.17]·2DMSO·H2O.

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Acknowledgments

The X-ray diffraction studies were performed by Irina Polyakova (deceased) at the Kurnakov Institute and were described by Dr. Sergey Nefedov (the Kurnakov Institute). The IR spectra of the compounds were measured by Ph. D. Lyudmila V. Goeva (the Kurnakov Institute).

Funding

The studies were performed within the framework of the State Assignment of the Kurnakov Institute (IGIC RAS) in the field of fundamental scientific research and was supported in part by the Russian Foundation for Basic Research (Russia), grant no. 20-03-00763. Synthesis of compounds was supported by the Council for Grants of the President of RF for State Support of scientific research performed by Young Russian Scientists (Grant MD-265.2019.3).

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Correspondence to Varvara V. Avdeeva.

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Malinina, E.A., Korolenko, S.E., Zhdanov, A.P. et al. Metal-Promoted Exopolyhedral Substitution of Terminal Hydrogen Atoms in the Closo-Decaborate Anion [B10H10]2– in the Presence of Copper(II): Formation of the Substituted Derivative [2-B10H9OH]2–. J Clust Sci (2020). https://doi.org/10.1007/s10876-020-01840-5

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Keywords

  • Decahydro-closo-decaborate anion
  • Boron clusters
  • Copper
  • Complexes
  • Substitution