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

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，以及设计新的转化来获得新产品。效率可以通过降低能源需求、减少所涉及的步骤数量、提高工艺选择性或简化产品分离和纯化来实现。这些特点都有助于降低生产的经济成本和环境影响。英国化工行业是英国经济的主要贡献者，年营业额为600亿英镑，维持50万个就业岗位，年贸易顺差为50亿英镑。当英国化工行业实施改进或新的催化过程时，将产生非常重大的影响。90%的化学品和药品在生产过程中都需要使用催化剂。催化剂的作用是将分子聚集在一起，并以更低的能量成本和更高的选择性进行转化。此外，在此过程中，催化剂是不变的，因此可以多次回收。因此，催化是设计更可持续的工艺的核心，这将减少对环境的影响，因为能够从替代的、更容易获得的原料开始，从而产生更高的效率，从而降低能源使用和减少浪费。本项目探索具有均相催化潜力的新型配合物的设计。均相催化剂通常包括一个单一的中心过渡金属，它作为反应的位置，并被许多配体包围，这些配体控制着反应的效率和选择性。最近已经设计出金属和配体都直接参与反应的协同催化剂。另一类协同催化剂的特点是两个金属中心串联工作，提供新的反应性和催化作用。这些新类型的催化剂都是从好奇心驱动的基础研究中出现的，并且已经扩大了可用于合成的催化剂池。这些已经被学术界和工业界的更多应用研究所采用，用于设计更高效和大规模的新催化过程。在这个项目中，我们将研究新一代的配合物，其中过渡金属（TM = Ru, Rh, Pt…）直接与主族金属（M' = Zn, Mg, Al…）结合。这两种金属中心的性质非常不同，在分离时它们促进的反应性和催化作用也非常不同。我们假设，这些新的“杂双金属”配合物结合在一起将促进新的反应性，否则无法获得。初步结果表明，我们有一个非常简单和非常通用的策略来合成这些新的TM-M'复合物，使用一套很容易，而且通常是商业上可用的构建块。因此，有可能产生大量新的TM-M'复合物。为了指导我们的工作，我们将结合实验化学方法和计算模型来了解这些杂双金属配合物是如何促进反应性的。然后，建模将用于预测稳定性和反应性，使我们能够将实验工作集中在那些具有最吸引人的特征（高反应性，高选择性等）的组合上。然后，我们将评估这些新配合物促进催化反应的能力，这样做将增加可用于学术界和工业界应用研究的催化剂池。

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.