Bélanger-Chabot Guillaume, Kaplan S Max, Deokar Piyush, Szimhardt Norbert, Haiges Ralf, Christe Karl O
Loker Hydrocarbon Research Institute, Department of Chemistry, University of Southern California, Los Angeles, CA, 90089-1661, USA.
Chemistry. 2017 Sep 21;23(53):13087-13099. doi: 10.1002/chem.201701690. Epub 2017 Aug 22.
The problem of preparing energetic, exclusively mono-azolyl substituted hydridoborate anions in high yield and purity from [BH ] and nitroazoles by hydrogen elimination was overcome by reacting the corresponding nitroazolate anions with the BH adducts BH ⋅S(CH ) or BH ⋅THF. The highly-energetic, nitro-, trinitromethyl-, and fluorodinitromethyl- substituted triazolyl- and tetrazolyl-trihydridoborate anions were synthesized in this manner and characterized by vibrational and multinuclear NMR spectroscopy and their crystal structures. The use of excess BH resulted in some cases in the addition of a second BH molecule bound more-weakly to one of the nitrogen atoms of the azole ring. All monoazolyl-trihydridoborates were thermally less stable than the parent azolate anions. A decomposition product of tetraphenylphosphonium (5-(trinitromethyl)-5H-2λ -tetrazol-2-yl)trihydridoborate, the tetraphenyl-phosphonium (dinitro-1H-tetrazol-5-yl)methanide monohydrate, was also structurally characterized, providing some insight into the decomposition pathways of the nitromethyl-substituted azolyltrihydridoborate anions.
通过使相应的硝基唑酸根阴离子与硼氢化钠加合物BH₃·S(CH₃)₂或BH₃·THF反应，克服了由[BH₄]⁻和硝基唑通过氢消除以高收率和纯度制备高能、仅单唑基取代的硼氢化物阴离子的问题。以这种方式合成了高能的、硝基、三硝基甲基和氟二硝基甲基取代的三唑基和四唑基三氢硼酸盐阴离子，并通过振动光谱和多核核磁共振光谱以及它们的晶体结构进行了表征。在某些情况下，使用过量的硼氢化钠会导致第二个硼氢化钠分子较弱地结合到唑环的一个氮原子上。所有单唑基三氢硼酸盐的热稳定性都低于母体唑酸根阴离子。还对四苯基鏻(5-(三硝基甲基)-5H-2λ⁵-四唑-2-基)三氢硼酸盐的分解产物四苯基鏻(二硝基-1H-四唑-5-基)甲烷一水合物进行了结构表征，这为硝基甲基取代的唑基三氢硼酸盐阴离子的分解途径提供了一些见解。
