Metal- and Nonmetal Boron Clusters: Synthetic, Chemical and Mechanistic Studies

硼氢化合物和这些含金属（金属硼烷）或碳（碳硼烷）的加合物表现出不同寻常的化学键类型，这对理论化学家非常感兴趣。这些化合物作为新型固态材料的前体也越来越重要。本项目是对硼化合物结构转化机理的持续研究。所获得的化学知识将指导金属硼烷的新合成路线的发展以及这些分子在其他化学领域的新应用。模型硼烷和杂原子硼烷簇的反应和重排机制将使用立体定向硼同位素标记作为主要诊断探针来确定。这方面的例子包括近碳硼烷和硝基六硼烷的重排研究，硼烷多烷基化的机理研究，以及三烷基锡氢化物还原硼卤素键过程中形成的长寿命中间体的表征。制备V族杂原子硼烷簇，建立其化学、光谱和结构特征。测定了几种含锌、含锰金属硼烷的反应范围。高硼含量聚合物的合成将在储能和固态材料方面得到发展。

Boron-hydrogen compounds and adducts of these containing metals (metalloboranes) or carbon (carboranes) exhibit unusual types of chemical bonds which are of considerable interest to theoretical chemists. These compounds are also of growing importance as precursors to new solid state materials. This project is a continuing investigation of the mechanisms of structural transformations of boron compounds. The chemical knowledge gained will guide the development of new synthetic routes to metalloboranes and new applications of these molecules in other areas of chemistry. The mechanisms of reactions and rearrangements of model borane and heteroatom borane clusters will be determined using stereospecific boron isotopic labeling as a primary diagnostic probe. Examples include rearrangement studies of closo-carboranes and nido- and arachno-hexaboranes, mechanistic studies of polyalkylation of boranes, and characterization of long lived intermediates formed during the reduction of boron- halogen bonds by trialkyltin hydrides. Group V heteroatom- borane clusters will be prepared and their chemical, spectroscopic and structural features established. The scope of reactivity of several classes of metalloboranes including some containing Zn and Mn will be determined. The syntheses of high boron content polymers will be developed for possible applications in energy storage and solid state materials.