Phosphine-Borane Dehydrocoupling: The Synthesis of Tailored New Materials through Mechanistic Studies of Catalytic Processes.

过渡金属催化的C-C、C-H或C-X键的生成或断裂反应是合成商品/原料化学品和精细化学品的基础。对这些过程的机制的阐明导致了具有基础、商业和社会重要性的重大突破（例如，新药物的路线、聚合物合成、具有令人兴奋的特性的新材料的合成、构建新分子的更有效和更绿色的方法）。相比之下，开发类似的催化途径来制备主族元素之间的键仍然是新生的。考虑到这些路线在合成新型聚合物、新材料、电子器件以及新的有机方法和合成生物活性分子方面的潜力，知识/技术方面的这种差距是显著的。最近，人们对第13/15族材料的催化脱氢偶联策略产生了浓厚的兴趣，原型为H3 B-NRRH和H3 B-PRRH（R =烷基，芳基，H），它们是新的氢输送系统或新型聚合物材料的前体。第13/15族聚合物相对未被开发，但作为聚合物全碳体系的类似物是重要的，其可能具有技术上有用的热物理、陶瓷前体和其他有用的材料性质。值得注意的是，缺乏一种统一的催化剂系统设计机械方法来定制生产此类材料。在这个项目中，我们将提供完整的脱氢偶联机理细节，并使用这些知识来设计，开发和实施催化剂系统，将产生新的膦硼烷（P/B）材料。我们的目标是有针对性地合成定义明确的新型单体，低聚物和聚合物膦硼烷，这将对未来的技术应用具有显着的潜力。

Transition-metal-catalysed reactions the make or break C-C, C-H or C-X bonds are cornerstone in the synthesis of commodity/feedstock chemicals and fine-chemicals. The elucidation of mechanism for such processes has led to major breakthroughs of fundamental, commercial and societal importance (e.g. routes to new pharmaceuticals, polymer synthesis, the synthesis of new materials with exciting properties, more efficient and greener ways to construct new molecules). By contrast the development of analogous catalytic routes to prepare bonds between main-group elements is still nascent. This gap in knowledge/technology is remarkable given the potential that such routes would have for the synthesis of novel polymers, new materials, electronic devices as well as new organic methodology and the synthesis of biologically active molecules. Recently there has been intense interest in catalytic dehydrocoupling strategies for group 13/15 materials, prototypically H3B-NRRH and H3B-PRRH (R = alkyl, aryl, H) that are precursors for new hydrogen-delivery systems or novel polymeric materials. Group 13/15 polymers are relatively unexplored, yet are important as analogues of polymeric all-carbon systems that could potentially have technologically useful thermophysical, pre-ceramic and other useful materials properties. Remarkably, lacking is a unified mechanistic approach to the design of catalyst systems that allows for the bespoke production of such materials. In this project we will provide full mechanistic details for dehydrocoupling and use this knowledge to design, develop and implement catalyst systems that will generate new phosphine-borane (P/B) materials. Our goal is the targeted synthesis of well-defined novel monomeric, oligomeric and polymeric phosphine-boranes that will have significant potential for future technological applications.