Borane Clusters: Synthetic and Mechanistic Investigations

在无机化学、生物无机化学和金属有机化学计划的支持下，唐纳德·F·盖恩斯博士将研究含硼簇合物分子的反应机理，并合成这类新分子。除了提供对这一重要化学领域的更深层次的理解外，这些结果还在能量存储和固态材料方面有潜在的应用。本项目将氢化硼簇合物及其衍生物的探索性合成研究与其形成、重排和反应机理的研究相结合。用立体特异的硼同位素标记作为诊断探针，结合B-10和B-11核磁共振光谱分析，将研究选定的硼烷和碳硼烷簇衍生物的反应和重排机理。将利用基于最近新的催化剂和烷基化试剂的各种方法，开发用于硼烷单烷基化和多烷基化的新路线和机械途径。对三烷基锡氢化物氢化还原硼卤键形成的长寿命中间体进行了表征。新型的含V族杂原子硼原子簇的制备将采用替代策略，例如同时插入硼和氮，这是最近用于制备新型含氮和含磷的硼烷簇的策略的扩展。

With support from the Inorganic, Bioinorganic and Organometallic Chemistry Program Dr. Donald F. Gaines will investigate the mechanisms of reactions of boron-containing cluster molecules and also synthesize new molecules of this type. In addition to providing a deeper understanding of this important area of chemistry, the results have potential applications in energy storage and solid state materials. This project combines exploratory synthetic investigations of boron hydride cluster molecules and their derivatives with investigations of the mechanisms of their formation, rearrangement and reactions. The mechanisms of reactions and rearrangements of selected derivatives of borane and carborane clusters will be investigated using stereospecific boron isotopic labeling as the diagnostic probe and B-10 and B-11 NMR spectroscopic analysis. New routes and mechanistic pathways for the mono- and polyalkylation of boranes will be developed using a variety of approaches based on recent new catalysts and alkylating agents. The long-lived intermediate formed during the hydridic reduction of boron-halogen bonds by trialkyltin hydrides will be characterized. Novel classes of group-V- containing heteroatom boron clusters will be prepared using alternative strategies such as simultaneous insertion of boron and nitrogen, extensions of the strategies used recently to prepare new types of nitrogen- and phosphorus-containing borane clusters.