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.

过渡金属催化的反应C-C、C-H或C-X键的形成或断裂是合成商品/原料化学品和精细化学品的基石。这些过程的机理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、具有令人兴奋的性能的新材料的合成、更高效和更绿色的构建新分子的方法)。相比之下，开发类似的催化路线来制备主族元素之间的键仍处于起步阶段。考虑到这种途径在合成新型聚合物、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，这种知识/技术方面的差距是显著的。最近，人们对13/15族材料的催化脱氢偶联策略产生了浓厚的兴趣，典型的H3B-NRRH和H3B-PRRH(R=烷基、芳基、H)是新的氢传递系统或新型聚合物材料的前体。13/15族聚合物相对未被探索，但作为聚合物全碳体系的类似物是重要的，这些体系可能具有潜在的技术上有用的热物理、预陶瓷和其他有用的材料性质。值得注意的是，缺乏一种统一的机械方法来设计催化剂系统，从而允许定制生产此类材料。在这个项目中，我们将提供脱氢偶联的完整机械细节，并利用这些知识来设计、开发和实施将产生新的膦-硼烷(P/B)材料的催化剂系统。我们的目标是有针对性地合成定义明确的新型单体、低聚和聚合膦-硼烷，这些化合物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

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

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