Synthesis, structure and reactivity of d- and f-block metal-aluminium heterobimetallic complexes

单金属、单位铂族金属催化剂在均相催化中占主导地位。最近，极化的异双金属配合物挑战了这一经典模式，因为它们能够在只有一个金属是氧化还原活性的两个金属位上离域激活/形成键。然而，合成有效的p-/d-嵌段混合催化剂的简便合成路线尚未实现。该项目旨在解决含有无载体的过渡金属(TM)、稀土(Ln)和吖系元素(AN)-铝键的配合物的合成挑战，并通过使用最先进的表征方法确定它们的电子结构，我们将开发结构引导的反应谱，以便在小分子活化化学中开发这类配合物。为了实现这一点，合成镁铝和锌铝异双金属配合物，这些配合物将被用来将铝片段转移到过渡金属，从而能够使用各种TM前体合成新的TM-Al配合物；由于这些起始原料容易获得，并且经常可以商业获得，因此确保了快速进展。根据电负性，新的Tm-Al络合物可分为两类：1)含有Al-Tm-+极化键的络合物；2)含有Al-+-Tm-极化键的络合物。这些不同的结合情景将促进不同的反应性和催化，这将相互补充和对比。合成一系列TM-Al络合物将使我们能够评估直接键合的Al中心对异双金属催化的影响范围，从不参与某些反应的旁观者配体到调整TM的电子性质的例子，与TM中心合作促进底物活化

Monometallic single-site platinum group metal catalysts predominate the homogeneous catalysis landscape. Recently, polarized heterobimetallic complexes are challenging this classical paradigm as they are capable of delocalizing bond activation/formation over two metal sites, where only one metal is redox active. However, facile synthetic routes to effective mixed p-/d-block catalysts have not yet been realized. This project aims to address this synthetic challenge for complexes containing unsupported transition metal (TM), lanthanide (Ln) and actinide (An)-aluminium bonds, and by determining their electronic structures using state-of-the-art characterization methods, we will develop structure-guided reactivity profiles in order to exploit this class of complex in small molecule activation chemistry.To achieve this, the synthesis of Mg-Al and Zn-Al heterobimetallic complexes and these will be used to transfer the Al fragment to transition metals enabling the synthesis of new TM-Al complexes using a variety of TM precursors; rapid progress is ensured as these starting materials are readily, and often commercially available. Based on electronegativities, the new TM-Al complexes can be divided into two categories: 1) complexes containing a Al--TM-+ polarized bond; and, 2) complexes bearing a Al-+-TM - polarized bond. These different bonding scenarios will promote divergent reactivity and catalysis that will complement and contrast each other. Synthetic access to a diverse range of TM-Al complexes will allow us to assess the range of effects that a directly bonded Al center can have on heterobimetallic catalysis, from spectator ligands that do not participate in some reactions, to examples that tune the electronic properties of the TM, cooperatively engaging with TM centres to facilitate substrate activation