碳十硼烷及其衍生物的反应性及应用

碳十硼烷(C₂B₁₀H₁₂)是由2个C原子和10个B原子组成的二十面体笼状结构大分子,有邻位、间位和对位三种异构体。碳十硼烷庞大的体积以及类芳香族三维刚性结构使它具有优异的高温稳定性和化学稳定性,良好的溶解性使其具有广泛而灵活的应用。本文总结了近年来碳十硼烷和碳十硼烷衍生物在C原子、B原子上的化学反应性以及在环加成和金属络合方面的研究。另外,由于碳十硼烷衍生物特殊的立体结构,优异的耐高温性、热氧化性及高硼含量,本文综述了碳十硼烷衍生物近年来在功能材料、催化剂及生物医药等多个领域的应用进展。

Chemistry and Application of Dicarbadodecaborane and Its Derivatives

Dicarba-closo-dodecaborane(carborane,C2B10H12) containing two carbon atoms and ten boron atoms adopts nearly icosahedral geometry in which the carbon and boron atoms are hexacoordinate.The compound exists as ortho-,meta-and para-isomers.Due to the strong electron-acceptor properties of the cluster,massive bulk and three-dimensional rigidity,carborane and its derivatives possess remarkable thermal and chemical stability.Besides,the ready solubility makes the compound and its derivatives widely applied.There are two common methods for synthesis of carborane and carborane derivatives,including the "alkyne insertion" methodology and the method based on the substitution reaction with carboranyl lithium.In this paper,the chemical reactions and functionalization of carborane and its derivatives are summarized,especially the substitution reactions on carbon atoms and boron atoms,the cycloaddition reaction and metal-carborane complexation.Futhermore,due to the excellent heat stability and high electronic delocalization,the carborane derivatives can be utilized as functional materials.Also,carborane derivatives can be applied in boron neutron capture therapy(BNCT) for the high boron content of carborane.Meanwhile,the metal-carborane complexes containing bulky carborane as ligands are reported to be available as the efficient catalysts.Herein,the advances in the application of the carborane derivatives in recent years are reviewed.