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New approaches to the synthesis of substituted derivatives of the [B3H8] anion

https://doi.org/10.32362/2410-6593-2024-19-1-61-71

Abstract

Objectives. To develop methods for the synthesis of substituted derivatives of the octahydrotriborate anion. Such compounds can be considered as hydrogen storage, components of ionic liquids, precursors for the production of boride coatings using the traditional chemical vapor deposition method, and also as a building material for the production of higher boron hydrogen clusters.

Methods. Since substitution reactions are sensitive to moisture and atmospheric oxygen, the syntheses were carried out in a direct flow of argon or in a dry, sealed SPEKS GB02M glove box with a double gas purification unit and two airlocks. The reaction was initiated by cooling to 0°C, in order to avoid the formation of by-products. All the results were characterized using infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies.

Results. The study presents a detailed study of the known methods for preparing substituted derivatives of the octahydrotriborate(1−) anion using dry hydrogen chloride as an electrophilic inductor and makes recommendations for improvement. In this method it is advisable to use cesium octahydrotriborate which facilitates the yield of the target product. New methods were proposed to initiate the substitution reaction in the [B3H8]-anion using N-chlorosuccinimide and bromine. Using these inductors, new substituted derivatives of the octahydrotriborate anion with N-nucleophiles were obtained and defined by means of IR and NMR spectroscopies: [B3H7NCR], (R = Et, i-Pr, Ph) and [B3H7NH2R], (R = C9H19 (INA), Bn), [B3H7NHEt2], as well as Bu4N[B3H7Hal], Bu4N[B3H6Hal2], where Hal = Cl, Br. It was also established that hydrogen bromide is released during the reaction with bromine and amines. This immediately protonates the amine which requires additional heating of the reaction mixture. The study also established that the reaction mechanism with N-chlorosuccinimide is not radical.

Conclusions. The main factors influencing the course of the substitution reaction are the possible occurrence of side interactions between the nucleophile and the inducer, steric possibilities, and subsequent isolation of the reactive reaction products.

About the Authors

A. A. Lukoshkova
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Anna A. Lukoshkova - Junior Researcher, Chemistry of Light Elements and Clusters Laboratory, Scopus Author ID 58781647200.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



A. T. Shulyak
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Alexandra T. Shulyak - Postgraduate Student, Junior Researcher, Chemistry of Light Elements and Clusters Laboratory, Scopus Author ID 57225000199.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



E. E. Posypayko
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Elizaveta E. Posypayko - Student.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



N. A. Selivanov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Nikita A. Selivanov - Cand. Sci. (Chem.), Researcher, Laboratory of Nanobiomaterials and Bioeffectors for Theranostics of Socially Significant Diseases, Scopus Author ID 57189441382, RSCI SPIN-code 2095-0956.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



A. V. Golubev
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Aleksey V. Golubev - Cand. Sci. (Chem.), Researcher, Laboratory of Nanobiomaterials and Bioeffectors for Theranostics of Socially Significant Diseases, Scopus Author ID 57215609169, RSCI SPIN-code 1591-7846.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



А. S. Kubasov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Aleksey S. Kubasov - Cand. Sci. (Chem.), Researcher, Chemistry of Light Elements and Clusters Laboratory, Scopus Author ID 56118634600, ResearcherID J-5588-2016.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



A. Yu. Bykov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Alexander Yu. Bykov - Cand. Sci. (Chem.), Senior Researcher, Chemistry of Light Elements and Clusters Laboratory, Scopus Author ID 17433685800, ResearcherID N-7157-2015.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



A. P. Zhdanov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Andrey P. Zhdanov - Cand. Sci. (Chem.), Researcher, Chemistry of Light Elements and Clusters Laboratory, Scopus Author ID 36350472200.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



K. Yu. Zhizhin
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences; MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian Federation

Konstantin Yu. Zhizhin - Dr. Sci. (Chem.), Corresponding Member of the Russian Academy of Sciences, Chief Researcher, Chemistry of Light Elements and Clusters Laboratory, IGIC RAS; Professor, Department of Inorganic Chemistry, M.V. Lomonosov IFCT, MIREA – RTU. Scopus Author ID 6701495620, ResearcherID C-5681-2013.

31, Leninskii pr., Moscow, 119991; 86, Vernadskogo pr., Moscow, 119571


Competing Interests:

The authors declare no conflicts of interest



N. T. Kuznetsov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
Russian Federation

Nikolay T. Kuznetsov - Dr. Sci. (Chem.), Academician of the Russian Academy of Sciences, Head, Chemistry of Light Elements and Clusters Laboratory. Scopus Author ID 56857205300, ResearcherID S-1129-2016.

31, Leninskii pr., Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest



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Supplementary files

1. Setup for the synthesis of [B3H7NCCH3]
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Type Исследовательские инструменты
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Indexing metadata ▾
  • The aim was to develop methods for the synthesis of substituted derivatives of the octahydrotriborate anion. Such compounds can be considered as hydrogen storage, components of ionic liquids, precursors for the production of boride coatings using the traditional chemical vapor deposition method.
  • The study presents a detailed study of the known methods for preparing substituted derivatives of the octahydrotriborate(1−) anion using dry hydrogen chloride as an electrophilic inductor and makes recommendations for improvement. In this method it is advisable to use cesium octahydrotriborate which facilitates the yield of the target product.
  • New methods were proposed to initiate the substitution reaction in the [B3H8]-anion using N-chlorosuccinimide and bromine.

Review

For citations:


Lukoshkova A.A., Shulyak A.T., Posypayko E.E., Selivanov N.A., Golubev A.V., Kubasov А.S., Bykov A.Yu., Zhdanov A.P., Zhizhin K.Yu., Kuznetsov N.T. New approaches to the synthesis of substituted derivatives of the [B3H8] anion. Fine Chemical Technologies. 2024;19(1):61-71. https://doi.org/10.32362/2410-6593-2024-19-1-61-71

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