Chemistry of C-Trimethylsilyl-Substituted Main Group Heterocarboranes

这个奖项来自无机、生物无机和有机金属化学项目，是在金属碳化学的一般领域。金属碳硼烷类化合物目前引起人们极大的兴趣，因为它们具有不同寻常的化学键类型，而且具有重要的实际意义，因为它们是重要的陶瓷的前体，可以用来合成具有有趣电性能的新材料。比如一维导体。该项目的主要重点是合成可能表现出有趣的结构、电学和光谱特性的扩展主基团杂碳硼烷体系。合成了新的主基团杂碳硼烷的电荷转移配合物并得到了它们的结构。对这些配合物特别感兴趣的是影响顶端杂原子滑移的因素，与这个顶端杂原子结合的配体的取向，以及配体碱度对簇键和结构的影响。还将探索先前关于M（II）插入的近碳烷和M（IV）夹在一起的共碳硼烷（M=Si和Ge）的工作所提出的化学新领域。这将包括合成几个多层堆叠硅、锗和混合硅/锗夹层配合物，并研究它们的电学性质。杂碳硼烷化学有待探索的最后一个领域是扩展、开发和发展主基团杂碳硼烷反应的直接合成方法，其中顶端杂原子主要与各种主基团和过渡金属发生非还原取代反应。

This award from the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the general area of metallacarboranechemistry. Metallacarborane compounds are of substantial current interest because of the unusual types of chemical bonds which they illustrate, and are also of practical importance because they are precursors to important ceramics and can be used to synthesize new materials with interesting electrical properties, such as one-dimensional conductors. The major emphasis of the project is the synthesis of extended main group heterocarborane systems that may exhibit interesting structural, electrical and spectral properties. New charge-transfer complexes of main group heterocarboranes will be synthesized and their structures obtained. Of particular interest for these complexes are the factors which influence the slippage of the apical heteroatom, the orientation of ligands bound to this apical heteroatom, and the effect of ligand basicity on cluster bonding and structure. Also to be explored are new areas of chemistry suggested by previous work on the M(II)-inserted closo- and M(IV)-sandwiched commo-carboranes (M=Si and Ge). This will include the synthesis of several multilevel stacked silicon, germanium and mixed silicon/germanium sandwiched complexes and a study of their electrical properties. The final area of heterocarborane chemistry to be explored is direct synthetic approaches to extend, exploit and develop reactions of main group heterocarboranes in which the apical heteroatom undergoes predominantly nonreductive substitution reactions with a variety of main group and transition metals.