Exploiting Synthetic and Structural Synergism in Alkali-Metal-Mediated Organotransitionmetallation (AMMO)

金属化反应，即氢与金属的交换，是最基本和最重要的化学变化之一，世界各地的学术和工业实验室每天都在进行。它在精细化学品、药品和聚合物的制造中特别有用。通常，在这些反应中使用的金属是锂，因为它具有高极性和高反应性。要将过渡金属连接到碳(芳香)骨架上，通常需要预先准备锂的衍生物，然后使用过渡金属盐进行金属交换反应。这是必要的，因为过渡金属通常不够活性，不足以直接连接到芳香族骨架上。然而，由于离子盐在共价有机溶剂中的溶解度问题和温度敏感性，这种交换反应的有效性受到限制。该项目将使这一领域发生革命性的变化，因为它将使碱金属介导的有机过渡金属(AMMO)这一新概念的发展成为可能。设计在同一分子中含有碱金属和过渡金属的试剂，可以产生独特的化合物，表现出碱金属化合物或过渡金属化合物本身(即单一金属体系)无法复制的特殊协同(混合金属)反应活性。因此，使用这些双金属试剂，现在可以直接将过渡金属中心连接到芳香族骨架上。我们构建了基于锂-锰和钠-锰体系的原型试剂，可以将锰直接结合到茂金属二茂铁的碳骨架上，从而验证了这一概念。拟议的创新计划将发展锰与其他一系列芳香有机化合物的协同碱金属化学，并率先将其用于其他重要的过渡金属，包括铬、铁、钴和镍。在芳香族框架内加入过渡金属，可以获得大量的性质组合(例如，氧化还原化学、磁化学和催化)，将打开传统锂基芳香族化合物范围之外的新化学机会的宝库。第一个过渡金属主体反冠大环(带有阳离子主环和阴离子客核的特殊环状化合物)将用氨气制备。据设想，根据过渡金属的不同，一些逆冠将显示出与已知的基于镁的逆冠完全不同的有趣的磁性和材料性质，因此是非磁性和非氧化还原活性的。

The metallation reaction, where hydrogen is exchanged for a metal, is one of the most fundamental and important chemical transformations, being practised everyday in academic and industrial laboratories across the world. It is particularly useful in the manufacture of fine chemicals, pharmaceuticals, and polymers. Usually the metal employed in these reactions is lithium because of its high polarity and high reactivity. To attach a transition metal to carbon (aromatic) frameworks one would normally have to prepare the lithium derivative beforehand, then carry out a metal exchange reaction using a transition metal salt. This is necessary because transition metals are not generally reactive enough to be directly attached to an aromatic framework. However, there are limits to the usefulness of such exchange reactions due to solubility problems of the ionic salt in covalent organic solvents and to temperature sensitivities. This project will revolutionise this area as it will enable the development of the new concept of alkali-metal-mediated organotransitionmetallation (AMMO). Designing reagents containing an alkali metal and a transition metal within the same molecule, can lead to unique compounds that exhibit special synergic (mixed-metal) reactivities which cannot be replicated by alkali metal compounds or by transition metal compounds on their own (i.e. the single metal systems). Consequently using these two-metal based reagents, it is now possible to directly attach transition metal centres to aromatic frameworks. We have built prototype reagents based on lithium-manganese and sodium-manganese systems which can directly attach manganese to the carbon framework of the metallocene ferrocene, thus proving the concept. The innovative programme proposed will develop the synergic alkali metal chemistry of manganese with a range of other aromatic organic compounds and pioneer the same for other important transition metals including chromium, iron, cobalt and nickel. Incorporating transition metals with access to a large portfolio of properties (for example in redox chemistry, magnetochemistry and catalysis) within aromatic frameworks, will open up a treasure chest of new chemical opportunities outside the scope of conventional lithium-based aromatic compounds. The first transition metal host inverse crown macrocycles (special cyclic compounds with cationic host rings and anionic guest cores) will be prepared using AMMO. It is envisaged that, depending on the transition metal, some inverse crowns will exhibit interesting magnetic and material properties radically different to those of known inverse crowns which are based on magnesium and are therefore non-magnetic and non-redox active.