A new convenient method for preparing tetrabutylammonium closo-dodecaborate

Authors

DOI:

https://doi.org/10.24959/ophcj.24.316264

Keywords:

closo-dodecaborate, octahydrotriborate, pyrolysis, DFT calculations

Abstract

A new synthetic procedure for preparing tetrabutylammonium closo-dodecaborate (Bu4N)2B12H12 by the solvent-free pyrolysis of tetrabutylammonium tetrahydroborate Bu4NBH4 has been developed. The procedure also provides isolation of pure tetrabutylammonium octahydrotriborate Bu4NB3H8 as a by-product. The main advantages of the route proposed are convenience and utilization of readily available starting materials. The compounds prepared have been characterized by NMR and IR spectroscopy. Based on the DFT calculations of normal modes of the [B3H8]- and [B12H12]2- anions, the assignment of the main absorption bands in the IR spectra of the compounds synthesized has been performed.

Supporting Agency

  • The work was supported by the National Research Foundation of Ukraine (grant No. 0123U104256).

Downloads

Download data is not yet available.

References

  1. Sivaev, I. B.; Bregadze, V. I.; Sjoberg, S. Chemistry of closo-dodecaborate anion [B12H12]2–: a review. Collect. Czech. Chem. Commun. 2002, 67, 679 - 727. https://doi.org/10.1135/cccc20020679.
    |
  2. Axtell, J. C.; Saleh, L. M. A.; Qian, E. A.; Wixtrom, A. I.; Spokoyny, A. M. Synthesis and applications of perfunctionalized boron clusters. Inorg. Chem. 2018, 57 (5), 2333 - 2350. https://doi.org/10.1021/acs.inorgchem.7b02912.
    | |
  3. Zhao, X.; Yang, Z.; Chen, H.; Wang, Z.; Zhou, X.; Zhang, H. Progress in three-dimensional aromatic-like closo-dodecaborate. Coord. Chem. Rev. 2021, 444, 214042. https://doi.org/10.1016/j.ccr.2021.214042.
    |
  4. Moss, R. L. Critical review, with an optimistic outlook, on Boron Neutron Capture Therapy (BNCT). Appl. Radiat. Isot. 2014, 88, 2 - 11. https://doi.org/10.1016/j.apradiso.2013.11.109.
    | |
  5. Zhang, X.; Lin, Y.; Hosmane, N. S.; Zhu, Y. Nanostructured boron agents for boron neutron capture therapy: a review of recent patents. Medical Review 2023, 3 (5), 425 - 443. https://doi.org/10.1515/mr-2023-0013.
    | |
  6. Miller, H. C.; Miller, N. E.; Muetterties, E. L. Chemistry of Boranes. XX. Syntheses of Polyhedral Boranes. Inorg. Chem. 1964, 3 (10), 1456 - 1463. https://doi.org/10.1021/ic50020a026.
  7. Miller, H. C.; Muetterties, E. L.; Boone, J. L.; Garrett, P.; Hawthorne, M. F. Borane Anions. In Inorg. Synth., 1967; pp 81 - 91. https://doi.org/10.1002/9780470132418.ch16.
  8. Adams, R. M.; Siedle, A. R.; Grant, J. Convenient Preparation of the Dodecahydrododecaborate Ion. Inorg. Chem. 1964, 3 (3), 461 - 461. https://doi.org/10.1021/ic50013a040.
  9. Sharon, P.; Afri, M.; Mitlin, S.; Gottlieb, L.; Schmerling, B.; Grinstein, D.; Welner, S.; Frimer, A. A. Preparation and characterization of bis(guanidinium) and bis(aminotetrazolium)dodecahydroborate salts: Green high energy nitrogen and boron rich compounds. Polyhedron 2019, 157, 71 - 89. https://doi.org/10.1016/j.poly.2018.09.055.
    |
  10. Bykov, A. Y.; Mal’tseva, N. N.; Generalova, N. B.; Zhizhin, K. Y.; Kuznetsov, N. T. Reactions of sodium tetrahydroborate with alkyl and aryl halides: A new approach to the synthesis of B3H8 and B12H122− anions. Russ. J. Inorg. Chem. 2013, 58 (11), 1321 - 1323. https://doi.org/10.1134/S003602361311003X.
    |
  11. Tran, B. L.; Allen, T. N.; Bowden, M. E.; Autrey, T.; Jensen, C. M. Effects of Glymes on the Distribution of Mg(B10H10) and Mg(B12H12) from the Thermolysis of Mg(BH4)2. Inorganics 2021, 9, 41. https://doi.org/10.3390/inorganics9060041.
    |
  12. Mishchenko, A. M.; Lishchenko, Y. L.; Kozytskiy, A. V.; Konysheva, K. M.; Satska, Y. A.; Ryabukhin, S. V.; Volochnyuk, D. M.; Kolotilov, S. V.; Rassukana, Y. V. Preparation of closo-decaborate by pyrolysis of tetraethylammonium borohydride: revision and optimization for large-scale production. ChemRxiv 2024. https://doi.org/10.26434/chemrxiv-2024-hrc1c.
  13. Hill, W. E.; Johnson, F. A.; Hosmane, N. S. From sodium borohydride to 1,2-dicarba-closo-dodecaboranes. Boron Chemistry–4. Plenary and Session Lectures Presented at the Fourth International Meeting on Boron Chemistry, Salt Lake City and Snowbird, Utah, USA, July 9-13, 1979. P. 33 - 39.
  14. Brändström, A.; Junggren, U.; Lamm, B. An improved method for the preparation of solutions of diborane. Tetrahedron Lett. 1972, 13 (31), 3173 - 3176. https://doi.org/10.1016/S0040-4039(01)93995-4.
    |
  15. Lyttle, D. A.; Jensen, E. H.; Struck, W. A. Simple Volumetric Assay for Sodium Borohydride. Anal. Chem. 1952, 24 (11), 1843 - 1844. https://doi.org/10.1021/ac60071a041.
  16. Barca, G. M. J.; Bertoni, C.; Carrington, L.; Datta, D.; De Silva, N.; Deustua, J. E.; Fedorov, D. G.; Gour, J. R.; Gunina, A. O.; Guidez, E.; Harville, T.; Irle, S.; Ivanic, J.; Kowalski, K.; Leang, S. S.; Li, H.; Li, W.; Lutz, J. J.; Magoulas, I.; Mato, J.; Mironov, V.; Nakata, H.; Pham, B. Q.; Piecuch, P.; Poole, D.; Pruitt, S. R.; Rendell, A. P.; Roskop, L. B.; Ruedenberg, K.; Sattasathuchana, T.; Schmidt, M. W.; Shen, J.; Slipchenko, L.; Sosonkina, M.; Sundriyal, V.; Tiwari, A.; Galvez Vallejo, J. L.; Westheimer, B.; Włoch, M.; Xu, P.; Zahariev, F.; Gordon, M. S. Recent developments in the general atomic and molecular electronic structure system. J. Chem. Phys. 2020, 152 (15). https://doi.org/10.1063/5.0005188.
    | |
  17. Chai, J.-D.; Head-Gordon, M. Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys. Chem. Chem. Phys. 2008, 10 (44), 6615 - 6620. https://doi.org/10.1039/B810189B.
    | |
  18. Schäfer, A.; Huber, C.; Ahlrichs, R. Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J. Chem. Phys. 1994, 100 (8), 5829 - 5835. https://doi.org/10.1063/1.467146.
    |
  19. Nainan, K. C.; Ryschkewitsch, G. E. A new synthesis of B3H8 ion. Inorganic and Nuclear Chemistry Letters 1970, 6 (9), 765 - 766. https://doi.org/10.1016/0020-1650(70)80095-2.
    |
  20. Bykov, A. Y.; Razgonyaeva, G. A.; Mal’tseva, N. N.; Zhizhin, K. Y.; Kuznetsov, N. T. A new method of synthesis of the B3H8 anion. Russ. J. Inorg. Chem. 2012, 57 (4), 471 - 473. https://doi.org/10.1134/S0036023612040055.
    |
  21. Deiseroth, H. J.; Sommer, O.; Binder, H.; Wolfer, K.; Frei, B. CsB3H8: Kristallstruktur und Optimierung der Synthese. Z. Anorg. Allg. Chem. 1989, 571 (1), 21 - 28. https://doi.org/10.1002/zaac.19895710102.
    |
  22. Chen, X.-M.; Ma, N.; Zhang, Q.-F.; Wang, J.; Feng, X.; Wei, C.; Wang, L.-S.; Zhang, J.; Chen, X. Elucidation of the Formation Mechanisms of the Octahydrotriborate Anion (B3H8) through the Nucleophilicity of the B–H Bond. J. Am. Chem. Soc. 2018, 140 (21), 6718 - 6726. https://doi.org/10.1021/jacs.8b03785.
    | |
  23. Chen, X.; Liu, X.-R.; Wang, X.; Chen, X.-M.; Jing, Y.; Wei, D. A safe and efficient synthetic method for alkali metal octahydrotriborates, unravelling a general mechanism for constructing the delta B3 unit of polyhedral boranes. Dalton Trans. 2021, 50 (39), 13676 - 13679. https://doi.org/10.1039/D1DT01892B.
    | |
  24. Dunbar, A. C.; Macor, J. A.; Girolami, G. S. Synthesis and Single Crystal Structure of Sodium Octahydrotriborate, NaB3H8. Inorg. Chem. 2014, 53 (2), 822 - 826. https://doi.org/10.1021/ic402127x.
    | |
  25. Drozdova, V. V.; Lisovskii, M. V.; Polyakova, I. N.; Zhizhin, K. Yu.; Kuznetsov, N. T. Interaction of closo-decaborate anion B10H102- with iminium salts. Russ. J. Inorg. Chem. 2006 51, 1552 - 1560.
  26. Sethio, D.; Daku, L. M. L.; Hagemann, H.; Kraka, E. Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−. ChemPhysChem 2019, 20 (15), 1967 - 1977. https://doi.org/10.1002/cphc.201900364.
    | |

Downloads

Published

2025-02-19

How to Cite

(1)
Mishchenko, A. M.; Nechayev, M. A.; Subota, A. I.; Kozytskiy, A. V.; Svaliavyn, O. V.; Lishchenko, Y. L.; Aleksandrova, A. M.; Rassukana, Y. V.; Leha, D. O. A New Convenient Method for Preparing Tetrabutylammonium Closo-Dodecaborate. J. Org. Pharm. Chem. 2025, 22, 3-9.

Issue

Section

Advanced Researches