New method for the synthesis of oxonium derivatives of closo-borate anions [BnHn]2-

  • Elena S. Boyarinova MIREA – Russian Technological University, Moscow, Russia
  • Danila V. Filin MIREA – Russian Technological University, Moscow, Russia
  • Elizaveta A. Yeshtukova-Shcheglova MIREA – Russian Technological University, Moscow, Russia http://orcid.org/0000-0002-3729-4466
  • Iliya E. Sokolov Federal Research Center for Nutrition, Biotechnology and Food Safety, Moscow, Russia
  • Artyom A. Medvedev Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow, Russi
  • Artemiy I. Nichugovskii MIREA – Russian Technological University, Moscow, Russia https://orcid.org/0000-0003-2523-2054
  • Evgeniy Yu. Matveev MIREA – Russian Technological University, Moscow, Russia https://orcid.org/0000-0003-0478-0705
DOI: https://doi.org/10.15328/cb1425
Keywords: boron cluster anions, closo-decaborate anion, closo-dodecaborate anion, synthesis of substituted derivatives, EINS, opening of cyclic substituents

Abstract

This work investigates the reaction of tetrabutylammonium salts of [B10H10]2- and [B12H12]2- anions with tetrahydrofuran, 1,4-dioxane, and tetrahydropyran in the presence of aqueous H[BF4] and H2[SiF6] solutions. It is shown that these reactions yield mono-substituted derivatives of the closo-decaborate anion ([2-B10H9O(CH2)4]-, [2-B10H9O(CH2)4О]-, [2-B10H9O(CH2)5]-) and closo-dodecaborate anion ([B12H11O(CH2)4]-, [B12H11O(CH2)4О]-, [B12H11O(CH2)5]-) in high yields. It was proven that in the case of the [B10H10]2- anion, the reaction proceeds regioselectively, leading specifically to products with substituents in the equatorial belt of the boron cluster. The closo-dodecaborate anion derivative with an exo-polyhedral tetrahydropyran substituent was further functionalized by reaction with potassium cyanide in DMF. Studies showed that this reaction results in the opening of the cyclic substituent, forming a derivative containing a pendant cyano group attached to the boron cluster via a pentamethylene spacer. This compound can be further modified at the terminal group to obtain biologically active boron-containing derivatives, promising for use in ¹⁰B-neutron capture therapy (BNCT) of malignant tumors, as well as antimicrobial and antiviral therapy.
The structures of all obtained derivatives were confirmed using a comprehensive set of modern physical and physicochemical analytical methods (elemental analysis, IR spectroscopy, multinuclear NMR spectroscopy, ESI mass spectrometry).

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Published
2025-06-29
How to Cite
Boyarinova, E., Filin, D., Yeshtukova-Shcheglova, E., Sokolov, I., Medvedev, A., Nichugovskii, A., & Matveev, E. (2025). New method for the synthesis of oxonium derivatives of closo-borate anions [BnHn]2-. Chemical Bulletin of Kazakh National University, 115(2), In Press. https://doi.org/https://doi.org/10.15328/cb1425
Issue
Vol 115 No 2 (2025): Chemical Bulletin of Kazakh National University (In Progress)
Section
Inorganic Chemistry
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