We propose several simple and effective methods for the synthesis of previously unknown trinitromethyl borohydrides and their complexes with simple cyclic ethers and aromatic nitrogen- containing heterocycles, whereas acyclic ethers did not form such complexes. The data from physicochemical investigations showed that these unique compounds contain directly linked oxidizing and reducing fragments. Some transformations of trinitromethylborane complexes were demonstrated, which can occur by cleavage of all types of bonds formed by boron atom in the starting compounds.
Similar content being viewed by others
Notes
Dedicated to Academician Yu. N. Bubnov on the occasion of his 80th birthday. For Preliminary Communication, see [1].
For spectral characterization of salt 2 at this stage, a quarter of the solution was concentrated by 2/3 under vacuum; the residue was dissolved in СН2Cl2 (15 ml). This procedure was repeated two more times, then cautiously evaporated under vacuum to dryness, the residue was dissolved in organic solvents and spectra were recorded.
This procedure occasionally resulted in detonations. To prevent that, we recommend to concentrate the reaction mixture by 2/3, dilute the residue with hexane (30 ml), decant the liquid from precipitate, dissolve the precipitate in benzene, filter, and evaporate the filtrate on a Petri dish, followed by recrystallization from Et2O–hexane mixture.
References
S. L. Ioffe, O. P. Shitov, and V. A. Tartakovskij, IMEBORON VIII – Eighth International Meeting on Boron Chemistry, July 11–15, 1993, Knoxville, Tennessee, USA, Program and abstracts (1993), p. 155.
H. C. Brown, Hydroboration, W. A. Benjamin Inc., New York (1962).
E. A. Lavrent'eva, G. V. Lagodzinskaya, M. L. Khidekel', O. P. Shitov, S. L. Ioffe, V. V. Negrebetskii, and V. A. Tartakovskii, Zh. Obsch. Khim., 43, 295 (1973).
G. Belanger-Chabot, M. Rahm, R. Haiges, and K. O. Christe, Angew. Chem., Int. Ed., 52, 11002 (2013).
O. P. Shitov, S. L. Ioffe, V. A. Tartakovskii, and S. S. Novikov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 21, 447 (1972). [Izv. Akad. Nauk SSSR, Ser. Khim., 21, 490 (1972).]
A. V. Kessenikh and V. V. Negrebetskii, Dokl. Akad. Nauk SSSR, 177, 1375 (1967).
A. Bellamy, The Infrared Spectra of Complex Molecules [Russian translation], Izd. Inostr. Lit., Moscow (1957).
S. A. Shevelev, L. I. Dalinger, V. M. Vinogradov, and A. A. Fainzil'berg, Bull. Acad. Sci. USSR, Div. Chem. Sci., 39, 1647 (1990). [Izv. Akad. Nauk SSSR, Ser. Khim., 39, 1816 (1990).]
This work was performed with financial support of the Russian Foundation for Basic Research (Grant # 15-03-05703).
The authors would like to express their gratitude to Corresponding Member of the Russian Academy of Sciences Yu. T. Struchkov and Candidate of Chemical Sciences A. А. Gusev for performing X-ray structural analysis of compound 7о and solving its structure.
The authors also acknowledge the assistance by Doctor of Chemical Sciences V. S. Bogdanov and Candidate of Chemical Sciences V. V. Negrebetskii in acquiring and interpreting the double boron-proton resonance spectra.
Author information
Authors and Affiliations
Corresponding author
Additional information
*Unpublished results of research by O. P. Shitov and S. L. Ioffe.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1795–1806, December, 2014.
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 503 kb)
Rights and permissions
About this article
Cite this article
Shitov, O.P., Tartakovskii, V.A. & Ioffe, S.L. Synthesis of Neutral and Charged Trinitromethyl Borohydrides and Their Complexes* . Chem Heterocycl Comp 50, 1647–1657 (2015). https://doi.org/10.1007/s10593-015-1634-4
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10593-015-1634-4