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

膦-硼烷脱氢偶联：通过催化过程的机理研究合成定制新材料。

• 批准号: EP/J02127X/1
• 负责人: Andrew Weller
• 金额: $ 45.13万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2012
• 资助国家: 英国
• 起止时间: 2012 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ02127X%2F1
• 关键词: Phosphine; Borane; Dehydrocoupling; Synthesis; Tailored

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.

过渡金属催化反应在综合商品/原料化学物质和精细化学物质的合成中，Make或brew c-c，c-c，c-h或c-x键是基石。阐明此类过程的机制已导致了基本，商业和社会重要性的重大突破（例如，通往新药物的途径，聚合物合成，具有令人兴奋的特性，更有效的新材料的合成，更有效的效率和更绿色的方式来构建新分子）。相比之下，在主组元素之间制备键的类似催化途径的发展仍然是偏生的。鉴于这种途径对于新型聚合物，新材料，电子设备以及新的有机方法论以及生物活性分子的合成的可能性和合成，因此知识/技术的这种差距非常出色。最近，人们对第13/15组材料，原型H3B-NRRH和H3B-PRRH（R =烷基，芳基，H）的催化脱氢策略引起了浓厚的兴趣，它们是新的氢交换系统或新型聚合物材料的前体。第13/15组聚合物相对尚未探索，但作为聚合物全碳系统的类似物很重要，这些系统可能具有技术有用的热物理，前陶瓷和其他有用的材料。值得注意的是，缺乏是一种统一的机械方法，用于设计催化剂系统，可以定制这种材料的生产。在这个项目中，我们将提供脱氢偶联的完整机械细节，并使用此知识来设计，开发和实施催化剂系统，从而生成新的磷酸 - 硼烷（P/B）材料。我们的目标是针对明确定义的新型单体，低聚和聚合物磷酸碳烷的有针对性合成，这将在未来的技术应用中具有巨大的潜力。

项目成果

Rhodium-Catalyzed Selective Partial Hydrogenation of Alkynes

• DOI: 10.1021/acs.organomet.5b00322
• 发表时间: 2015-06
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Jingwei Luo;Robin Theron;Laura J. Sewell;T. Hooper;A. Weller;A. Oliver;J. McIndoe

Effect of the phosphine steric and electronic profile on the Rh-promoted dehydrocoupling of phosphine-boranes.

• DOI: 10.1021/ic500032f
• 发表时间: 2014-04-07
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Hooper TN;Huertos MA;Jurca T;Pike SD;Weller AS;Manners I
• 通讯作者: Manners I

The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes.

BN-环己烷的 Sigma 配合物的合成、表征和脱氢。

• DOI: 10.1002/chem.201502986
• 发表时间: 2016-01-04
• 期刊: Chemistry (Weinheim an der Bergstrasse, Germany)
• 作者: Kumar A;Ishibashi JS;Hooper TN;Mikulas TC;Dixon DA;Liu SY;Weller AS
• 通讯作者: Weller AS

Oligomeric aminoborane precursors for the chemical vapour deposition growth of few-layer hexagonal boron nitride

• DOI: 10.1039/c6ce02006b
• 发表时间: 2017-01
• 期刊: CrystEngComm
• 影响因子: 3.1
• 作者: Xiaochen Wang;T. Hooper;Amit Kumar;Isobel K. Priest;Yuewen Sheng;Thomas O. M. Samuels;Shanshan Wang;A. Robertson;M. Pacios;H. Bhaskaran;A. Weller;J. Warner