Selective synthesis of the B11H14− and B12H122− borane derivatives and the general mechanisms of the B-H bond condensation
Selective synthesis of the B11H14− and B12H122− borane derivatives and the general mechanisms of the B-H bond condensation
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DOI：
10.1007/s11426-023-1852-9
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发表时间：
2023-12
期刊：
影响因子：
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通讯作者：
Yi Jing;Xinghua Wang;Hui Han;Xin-Ran Liu;Xing-Chao Yu;Xi-Meng Chen;Donghui Wei;Lai-Sheng Wang;Xuenian Chen
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文献类型：
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作者：
Yi Jing;Xinghua Wang;Hui Han;Xin-Ran Liu;Xing-Chao Yu;Xi-Meng Chen;Donghui Wei;Lai-Sheng Wang;Xuenian Chen
多面体硼烷是一类众所周知的硼分子簇，具有独特的物理和化学性质，在过去的几十年里，人们一直在努力寻找更有效的合成方法。然而，由于对合成多面体硼烷至关重要的B-H键缩合反应机理尚不清楚，现有的合成方法存在效率低、选择性低的问题。在这里，我们报道了高选择性和高效的合成方法十四氢十二硼酸盐（1 -）（B11H14−）和十二氢十二硼酸盐（2 -）（B12H122−）阴离子，采用市售和廉价的原料。对反应机理进行了理论和实验研究。我们发现B-H键凝聚的本质是二氢键相互作用，其中带正电的氢（桥接氢）起着至关重要的作用。本研究不仅为B11H14 -和B12H122 -的合成提供了更有效和选择性的方法，而且揭示了B-H键缩合的性质和多面体硼烷的一般形成机制。这一发现将有助于开发更有效的多面体硼烷合成方法并促进其广泛应用。
Polyhedral boranes are a class of well-known boron molecular clusters with unique physical and chemical properties, and great efforts have been made in the past decades to find more effective synthetic methods. However, the established synthetic methods suffer from low efficiency and low selectivity because the mechanism of the B–H bond condensation reaction, critical for the synthesis of the polyhedral boranes, is not well understood. Here we report highly selective and efficient synthetic methods of the salts of the tetradecahydridoundecaborate (1–) (B11H14−) and dodecahydrido-dodecaborates (2–) (B12H122−) anions by employing commercially available and inexpensive starting materials. Both theoretical and experimental investigations are carried out to elucidate the reaction mechanisms. We have found that the nature of the B–H bond condensation is the dihydrogen bonding interaction in which the positively charged hydrogens (bridged hydrogens) play a crucial role. The current study has not only led to more effective and selective synthetic methods for B11H14−and B12H122−but also unveiled the nature of the B–H bond condensation and the general formation mechanisms of polyhedral boranes. This finding will facilitate the development of more effective synthetic methods for polyhedral boranes and spur their wide application.