Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

极性有机金属化学为惰性键转化为活性键以制造新化合物和新材料提供了必要的工具。很少有芳香分子（如药品、农用化学品、香水）在制造过程中不经过极性有机金属化学处理的。尽管这种化学有着悠久而成功的历史，但它目前正处于令人兴奋的发展十字路口，其中看似不可能的挑战现在即将成为可能。该项目旨在从根本上改革极性有机金属化学的实践，使其更适合空气和水分，更环保，更节约原子和可持续发展。重点研究采用共络合工艺制备的新型s-嵌段金属多组分试剂的合成、培养和开发。初步研究表明，在相同的环境中混合不同的组分（例如，两种不同的金属配合物；或一种金属，但配体的分类）可以导致有用的协同效应，而非混合系统是不可能的。因此，化学的范围和构建新化合物和新材料以满足社会需求的能力大大扩大了。基于地球上丰富的金属，这些共络合试剂将在关键的有机转化中进行筛选，重点是脱质子金属化和金属-卤素交换反应，以及针对合成相关有机底物的串联C-C键形成方法（作为更昂贵和更不环保的过渡金属介导方法的替代方法）。化学计量反应将升级为催化机制，以建立s-block协同催化的基本规则，重点关注一系列不饱和分子的分子内氢胺化反应。该项目的一个关键目标是开拓和推广在深共晶溶剂（DESs）中使用多组分极性有机金属试剂。这些DESs将为那些挥发性有机溶剂（VOC）提供更具成本效益，更环保和生物可再生的反应介质，而目前大多数极性有机金属化学都是在这些溶剂中进行的。这一目标的进展将大大有助于最终实现极性有机金属化学中“不可能”的挑战，即在空气和/或水介质中合成和利用化学选择性有机金属试剂。不需要干燥的惰性气氛将对学术界和工业界的极性有机金属化学实践产生真正的世界性影响。

Polar organometallic chemistry provides an essential toolkit for transforming inert bonds into reactive bonds to make new compounds and materials. Very few aromatic molecules (e.g., pharmaceuticals, agrochemicals, perfumes) are made without polar organometallic chemistry being practiced at some stage in their manufacture. Though this chemistry has a long and successful history, it is currently at an exciting crossroads in its development with seemingly impossible challenges within it now on the verge of becoming possible. This project is designed towards fundamentally reforming the practice of polar organometallic chemistry making it more air and moisture compatible, greener, more atom-economical and sustainable. Research will focus on the synthesis, cultivation and exploitation of new s-block metal multicomponent reagents made by co-complexation protocols. Preliminary work has shown that mixing different components within the same environment (for example, two distinct metal complexes; or one metal but with an assortment of ligands) can lead to useful synergistic effects not possible with unmixed systems. The scope of the chemistry and the ability to construct new compounds and new materials to meet societal needs are thus greatly broadened. Based on earth-abundant metals, these co-complex reagents will be screened in key organic transformations, focusing on deprotonative metallation and metal-halogen exchange reactions as well as in tandem C-C bond forming methods (as an alternative to more expensive and less environmentally benign transition-metal-mediated approaches) targeting synthetically relevant organic substrates. Stoichiometric reactions will be upgraded to catalytic regimes to establish the ground rules for s-block synergistic catalysis focusing on intramolecular hydroamination reactions of a range of unsaturated molecules. A key objective of the project is to pioneer and extend the use of multicomponent polar organometallic reagents in Deep Eutectic Solvents (DESs). These DESs will provide more cost-effective, greener and biorenewable reaction media to those volatile organic solvents (VOC's) in which most polar organometallic chemistry is carried out today. Progress in this aim will go a long way to eventually realising the "impossible" challenge in polar organometallic chemistry of synthesising and utilising chemoselective organometallic reagents under air and/or in aqueous media. Dispensing with the need for a dry inert atmosphere would have genuine worldwide implications for the practice of polar organometallic chemistry both in academia and industry.