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Dual Unsaturated Transition Metal-Main Group (TM-M') Heterobimetallic Complexes for Cooperative Reactivity and Catalysis

用于协同反应和催化的双不饱和过渡金属主族（TM-M）异双金属配合物

基本信息

批准号：
EP/T019743/1
负责人：
Mike Whittlesey
金额：
$ 54.42万
依托单位：
University of Bath
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2020
资助国家：
英国
起止时间：
2020 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FT019743%2F1
关键词：
Dual Unsaturated Transition Metal Main

项目摘要

The transformation of organic molecules is central to the production of the commodities, materials and fine chemicals (such as pharmaceuticals) that underpin modern society. Much research in academic and industrial chemistry is focused on improving the processes by which these products are formed, as well as on designing new transformations to access new products. Efficiencies can be achieved by lowering energy requirements, reducing the number of steps involved, improving process selectivities, or simplifying product separation and purification. These features all serve to reduce the economiccosts and environmental impact of production. Improved or new catalytic processes have a very significant impact when implemented by the UK chemicals sector, a major contributor to the UK economy that has an annual turnover of £60 billion, sustains 500,000 jobs and an annual trade surplus of £5 billion.>90% of chemicals and pharmaceuticals involve the use of a catalyst in their manufacture. Catalysts work by bringing molecules together and enabling their transformation with reduced energy costs and often improved selectivity. Moreover, the catalyst is unchanged in this process and so can be recycled many times. Catalysis is therefore central to the design of more sustainable processes that will have reduced environmental impact, as greater efficiency results from the ability to start from alternative, more readily available feedstocks, leads to lower energy usage and reductions in waste.This project explores the design of new complexes with potential in homogeneous catalysis. Homogeneous catalysts generally involve a single central transition metal which acts as the site of reaction and which is surrounded by a number of ligands that control the efficiency and selectivity of the process. More recently cooperative catalysts have been designed where both the metal and a ligand participate directly in the reaction. Another class of cooperative catalyst features two metal centres working in tandem to provide new reactivity and catalysis. These new classes of catalyst have all emerged from curiosity-driven, fundamental research and have served to broaden the pool of catalysts available for applications in synthesis. These have then been taken on by more applied research in academia and industry to exploit in the design of more efficient and new catalytic processes at scale.In this project we will study a new generation of complexes in which a transition metal (TM = Ru, Rh, Pt...) is directly bound to a main group metal (M' = Zn, Mg, Al...). The properties of these two types of metal centres are very different and in isolation they promote very different reactivity and catalysis. We hypothesize that in combination these new 'heterobimetallic' complexes will promote new reactivity that cannot otherwise be accessed. Preliminary results have shown that we have a very simple and extremely general strategy to the synthesis of these new TM-M' complexes using a suite of building blocks that are readily, and often commercially, available. There is therefore the potential to make a very large number of new TM-M' complexes. In order to guide our work, we will combine an experimental chemistry approach with computational modelling to provide an understanding how these heterobimetallic complexes promote reactivity. Modelling will then be used to predict stability and reactivity, allowing us to focus our experimental work on those combinations with the most attractive features (high reactivity, high selectivity etc.). We will then assess the ability of these new complexes to promote catalytic reactions and in doing so will add to the pool of catalysts that are available for possible exploitation by applied research in academia and industry.

有机分子的转化对于支撑现代社会的商品、材料和精细化学品（如药品）的生产至关重要。学术和工业化学的许多研究都集中在改进这些产品形成的过程，以及设计新的转化以获得新产品。可以通过降低能量需求、减少所涉及的步骤数量、提高工艺选择性或简化产物分离和纯化来实现效率。这些功能都有助于降低生产的经济成本和环境影响。改进的或新的催化工艺在英国化学品行业实施时会产生非常重大的影响，该行业是英国经济的主要贡献者，年营业额为600亿英镑，维持50万个工作岗位和50亿英镑的年贸易顺差。90%的化学品和药品在生产过程中使用催化剂。催化剂的工作原理是将分子聚集在一起，使它们能够以更低的能源成本和更高的选择性进行转化。此外，催化剂在此过程中没有变化，因此可以多次循环使用。因此，催化是设计更可持续的工艺的核心，这种工艺将减少对环境的影响，因为从替代的、更容易获得的原料开始的能力会带来更高的效率，从而导致更低的能源使用和减少浪费。该项目探索了具有均相催化潜力的新型复合物的设计。均相催化剂通常涉及单个中心过渡金属，其充当反应位点并且被控制该方法的效率和选择性的许多配体包围。最近，已经设计了金属和配体直接参与反应的协同催化剂。另一类协同催化剂的特征在于两个金属中心串联工作，以提供新的反应性和催化作用。这些新型催化剂都是从好奇心驱动的基础研究中产生的，并扩大了可用于合成的催化剂的范围。这些都被学术界和工业界的更多应用研究所采用，以设计更有效的新催化过程。在这个项目中，我们将研究新一代的络合物，其中过渡金属（TM = Ru，Rh，Pt.）直接与主族金属（M ′ = Zn、Mg、Al.）结合。这两种类型的金属中心的性质是非常不同的，并且孤立地，它们促进非常不同的反应性和催化作用。我们假设，在组合这些新的“杂环”复合物将促进新的反应，否则不能访问。初步结果表明，我们有一个非常简单和非常普遍的策略来合成这些新的TM-M'复合物，使用一套容易，通常是商业上可获得的结构单元。因此，存在制备非常大量的新的TM-M'复合物的潜力。为了指导我们的工作，我们将结合联合收割机的实验化学方法与计算建模，以提供一个了解这些杂环化合物如何促进反应。然后将使用建模来预测稳定性和反应性，使我们能够将实验工作集中在具有最具吸引力特征（高反应性，高选择性等）的组合上。然后，我们将评估这些新络合物促进催化反应的能力，并在这样做的过程中，将增加可用于学术界和工业界应用研究的催化剂库。