Amine-Borane Dehydropolymerisation for the Synthesis and Exploitation of Polyaminoboranes as Routes to New BN-Containing Materials

聚氨基硼烷-(H2BNHR)n-是与聚烯烃-(H2CCHR)n-密切相关的主链B-N -骨架的聚合物。然而，它们的基本材料和化学性质基本上尚未被探索，尽管它们有可能作为高性能硼基陶瓷和六氮化硼的可加工前体。这是因为目前还缺乏一种具有挑战性的高效和强大的有机金属催化剂系统，这种系统可以使聚合物的分子量和分散性可控。然而，Weller实验室最近的研究结果表明，在理解和利用有机金属催化剂的设计和机制方面取得了重大进展，并且“有序”控制胺-硼烷脱氢聚合现在是可能的。该博士学位的雄心勃勃的目标是开发强大的、可扩展的、定制的聚氨基硼烷路线，从而允许其更广泛的材料开发。新的第9组（Co, Rh, Ir）过渡金属催化剂体系将被合成并探索用于聚合物合成令人兴奋的新型“BN”聚合物材料，通过机制主导的设计策略。通过针对控制聚合物链长和分散性、成本和使用实用性的理想指标，将开发出大规模运行的催化剂系统。将这些推进到材料发现中，将探索允许使用这些聚合物作为新材料分子前体的用户友好方法。低温处理将产生各种令人兴奋的新型“氮化硼”材料，其中聚合物特性（使用开发的催化剂）将有助于确定所得到的技术重要材料的材料特性，特别是3D氮化硼材料：六方氮化硼和硼碳氮化硼具有非常有趣的光学，电子，热学和化学特性。将会有一个创新的循环，在材料化学方面有希望的线索导致新的和已知的催化剂系统的改进。该项目是由Andrew Weller（约克，催化）和Richard Douthwaite博士（约克，无机材料合成和表征）的团队合作完成的。博士生将成为广泛技术方面的专家，这将使他们能够开发新的有机金属催化剂系统（合成），详细的动力学和机制研究，然后将这些应用于材料合成和表征。特别的技能将发展：有机金属合成，催化机制的阐明，核磁共振波谱，x射线晶体学和材料合成和表征技术。在博士学位结束时，候选人将在广泛的基础和更多应用的有机金属/无机材料化学技术方面拥有广泛而深入的专业知识。

Polyaminoboranes, -(H2BNHR)n-, are polymers with main-chain B-N backbones that are closely related to polyolefins, -(H2CCHR)n-. However, their fundamental materials and chemical properties are essentially unexplored, despite potential applications as processable precursors to high-performance boron-based ceramics and hex-boron nitride. This is because the challenging combination of efficient and robust organometallic catalyst systems that give polymer of controllable molecular weight and dispersity is missing. However, recent results from the Weller lab have demonstrated a significant advance in understanding and harnessing both organometallic catalyst design and mechanism, and the controlled amine-borane dehydropolymerisation "to order" is now a possibility. The ambitious objectives of this PhD are to develop robust, scalable, routes to bespoke polyaminoboranes, that allows for their wider materials exploitation. New group 9 (Co, Rh, Ir) transition metal catalyst systems will be synthesised and explored for polymer synthesis of exciting new "BN" polymeric materials, through a mechanism-led design strategy. By targeting the desirable metrics of control of polymer chain length and dispersity and cost and practicality of use, catalyst systems that operate on larger scale will be developed. Taking these forward into materials discovery, user friendly methods that allow for the use of these polymers as molecular precursors to new materials will be explored. Low temperature processing will lead to a variety of exciting new "BN" materials where the polymer characteristics (using the catalysts developed) will help define the materials properties of the resulting technologically important materials, especially 3D BN materials: hexagonal boron nitride and boron carbon nitride have very interesting optical, electronic, thermal and chemical properties. There will be a cycle of innovation, with promising leads in materials chemistry leading to the refinement of new and known catalyst systems. The project is collaborative between the groups of Andrew Weller (York, catalysis) and Dr Richard Douthwaite (York, inorganic materials synthesis and characterisation). The PhD student will become expert in a wide range of techniques, that will allow them to develop new organometallic catalyst systems (synthesis), detailed kinetics and mechanism studies, and then take these through to materials synthesis and characterisation. In particular skills will be developed in: organometallic synthesis, elucidation of mechanism in catalysis, NMR spectroscopy, x-ray crystallography and materials synthesis and characterisation techniques. At the end of the PhD the candidate will have broad and deep expertise in a wide range of fundamental, and more applied, organometallic/inorganic materials chemistry techniques.