Preparation of closo-decaborate by pyrolysis of tetraethylammonium borohydride: Revision and optimization for large-scale production

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2025-06-25 DOI:10.1016/j.poly.2025.117646

Artem M. Mishchenko , Yulian L. Lishchenko , Andriy V. Kozytskiy , Kateryna M. Konysheva , Yulia A. Satska , Serhiy V. Ryabukhin , Dmytro M. Volochnyuk , Sergey V. Kolotilov , Yuliya V. Rassukana

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Abstract

Several methods for the preparation of closo-decaborate ([B₁₀H₁₀]²⁻ as polyalkylammonium salts) – a key compound for the synthesis of carborane – by pyrolysis of tetraethylammonium borohydride were examined. The studied reactions included variations in decomposition temperature, liquid medium, pressure and reaction time. The products were analyzed by ¹¹B and ¹H NMR spectroscopy, and, in some cases, by IR-spectroscopy. It was found that pyrolysis of Et₄NBH₄ in suspension in silicone fluid led to the mixtures of (Et₄N)₂[B₁₀H₁₀] and (Et₄N)₂[B₁₂H₁₂]. Pyrolysis of Et₄NBH₄ in n-decane or decalin resulted in Et₄N[B₃H₈] as a primary product. An increase of reaction time in n-decane or both time and temperature in decalin yielded the mixture of (Et₄N)₂[B₁₀H₁₀], (Et₄N)₂[B₁₂H₁₂] and other compounds. It was shown that the degree of conversion of Et₄NBH₄ into Et₄N[B₃H₈] on time in n-decane at 174 °C and decalin at 180 °C linearly depends on time. Several methods for purification of closo-decaborate from other pyrolysis products were checked. A synthetic procedure for preparation of closo-decaborate from 60 g of Et₄NBH₄ was proposed, yielding 2.85 g of (Bu₃NH)₂[B₁₀H₁₀] (95 % purity) in one run.

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硼氢化四乙基铵热解制备近癸酸盐：大规模生产的修正与优化

研究了四乙基硼氢化铵热解合成碳硼烷的关键化合物——近癸酸盐（[B10H10]2 - as聚烷基铵盐）的几种制备方法。所研究的反应包括分解温度、液体介质、压力和反应时间的变化。产物通过11B和1H NMR谱分析，在某些情况下，通过ir谱分析。研究发现，悬浮态Et4NBH4在有机硅液中热解生成（Et4N）2[B10H10]和（Et4N）2[B12H12]的混合物。Et4NBH4在正癸烷或十氢化萘中热解生成主要产物Et4N[B3H8]。在正十烷中增加反应时间或在十烷中增加反应时间和温度，可以得到（Et4N）2[B10H10]、（Et4N）2[B12H12]等化合物的混合物。结果表明，在174℃的正癸烷和180℃的十萘中，Et4NBH4及时转化为Et4N[B3H8]的程度与时间呈线性关系。考察了几种从其他热解产物中提纯近癸酸盐的方法。提出了一种以60 g Et4NBH4为原料，一次可制得（bu3nh2 [B10H10]） 2.85 g（纯度95%）的合成方法。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.