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

金属化反应是将氢转化为金属的反应，是最基本、最重要的化学转化之一，在世界各地的学术和工业实验室中每天都在进行。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。为了将过渡金属连接到碳（芳香）框架上，通常必须事先准备锂衍生物，然后使用过渡金属盐进行金属交换反应。这是必要的，因为过渡金属通常没有足够的反应性，不能直接附着在芳香骨架上。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问题，这种交换反应的有效性受到限制。该项目将彻底改变这一领域，因为它将使碱金属介导的有机过渡金属化（AMMO）的新概念得以发展。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，这些化合物表现出特殊的协同（混合金属）反应活性，这是碱金属化合物或过渡金属化合物本身（即单金属体系）无法复制的。因此，使用这些基于双金属的试剂，现在可以直接将过渡金属中心连接到芳香框架上。我们已经建立了基于锂锰和钠锰系统的原型试剂，可以直接将锰附着在茂金属二茂铁的碳框架上，从而证明了这一概念。提出的创新方案将开发锰与一系列其他芳香有机化合物的协同碱金属化学，并在其他重要过渡金属（包括铬、铁、钴和镍）方面开创同样的先河。将过渡金属与芳香族框架内的大量特性（例如氧化还原化学，磁化学和催化）相结合，将在传统的锂基芳香族化合物范围之外开辟新的化学机会的宝库。第一个过渡金属宿主逆冠大环（带有阳离子宿主环和阴离子客体核的特殊环状化合物）将用AMMO制备。据设想，根据过渡金属的不同，一些逆冠将表现出有趣的磁性和材料性质，与那些基于镁的已知逆冠完全不同，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.