Polyborane Syntheses and Reactions

宾夕法尼亚大学化学系的Larry Sneddon博士得到了化学部无机、生物无机和有机物项目的支持，致力于开发新的通用方法，用于系统、高产率地合成聚硼烷化合物和聚合物。拟议的工作将导致新的离子液体为基础的方法，用于合成和改性的聚硼烷;金属催化的聚硼烷硼氢化，反式硼化，和烯基聚硼烷复分解反应;和路线，通过早期的金属催化的烯基聚硼烷聚合和铼催化的烯基聚硼烷开环复分解聚合（ROMP）反应。这些研究将强调发现新的反应，并了解其基本步骤和控制因素。新的反应将使重要的新的烷基和烯基聚硼烷，碳硼烷和连接的聚硼烷分子化合物的系统合成，以及具有潜在的技术用途的全新类型的混合“聚硼烷-无机”和“聚硼烷-有机”聚合物材料。理解金属-聚硼烷相互作用的本质对于发现和控制新的金属催化反应具有根本的重要性;因此，该项目的另一个中心目标是更好地理解聚硼烷和金属聚硼烷的结构、键合、反应机理和性质。聚硼烷化合物具有重要的性质，这些性质引起了从用作癌症试剂，高温聚合物、燃烧速率调节剂、核废料萃取剂、陶瓷前体和弱配位阴离子。然而，这些和其他潜在用途的开发，以及该领域的进一步科学发展，由于不能有效地合成和修饰这些化合物而受到严重阻碍。显然需要合理的、选择性的、高产率的反应方法。该项目将教育有创造力和技能的青年科学家，其中包括妇女和代表性不足的少数民族。

Dr. Larry Sneddon, Department of Chemistry, University of Pennsylvania, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Divisionto develop new general methodologies for the systematic, high-yield syntheses of polyborane compounds and polymers. The proposed work will result in new ionic-liquid based methods for the synthesis and modification of polyboranes; metal-catalyzed polyborane hydroboration, dehydrogenative-borylation, and alkenylpolyborane metathesis reactions; and routes to poly(organopolyborane) polymers via both early metal catalyzed alkenylpolyborane polymerization and ruthenium-catalyzed alkenylpolyborane ring opening metathesis polymerization (ROMP) reactions. The studies will emphasize the discovery of new reactions and the development of an understanding of their fundamental steps and controlling factors. The new reactions will enable the systematic synthesis of important new alkyl- and alkenylpolyborane, carborane and linked-polyborane molecular compounds, and totally new types of hybrid "polyborane-inorganic" and "polyborane-organic" polymeric materials that have potential technological uses. Understanding the nature of metal-polyborane interactions is of fundamental importance to the discovery and control of new metal catalyzed reactions; therefore, a further central goal of this project is to achieve a better understanding of the structures, bonding, reaction mechanisms, and properties of both polyboranes and metallapolyboranes.Polyborane compounds have important properties that give rise to applications ranging from uses as cancer agents, high temperature polymers, burn rate modifiers, extractants for nuclear wastes, ceramic precursors and weakly coordinating anions. However, the exploitation of these and other potential uses, as well as the further scientific development of the field, has been seriously hampered by the inability to efficiently synthesize and modify such compounds. There is a clear need for rational, selective, high yield reaction methods. The project will educate creative and skilled young scientists, which will include women and under represented minorities.