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

d-和f-嵌段金属-铝异双金属配合物的合成、结构和反应性

• 批准号: 2856970
• 金额: --
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2856970
• 关键词: Synthesis; structure; reactivity; block; metal

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

单中心铂族金属催化剂在均相催化领域占主导地位。最近，极化的杂环化合物正在挑战这一经典范式，因为它们能够在两个金属位点上离域键活化/形成，其中只有一种金属是氧化还原活性的。然而，有效的混合p-/d-嵌段催化剂的简易合成路线尚未实现。该项目旨在解决含有无支撑过渡金属（TM）、镧系元素（Ln）和锕系元素（An）-铝键的复合物的合成挑战，并通过使用最先进的表征方法确定其电子结构，我们将开发结构指导的反应性概况，以便在小分子活化化学中利用这类复合物。合成Mg-Al和Zn-Al杂原子络合物，这些将用于将Al片段转移到过渡金属，使得能够使用各种TM前体合成新的TM-Al络合物;由于这些起始材料容易且通常可商购获得，因此确保了快速进展。根据电负性，新的TM-Al配合物可分为两类：1）含有Al-TM-+极化键的配合物; 2）含有Al-+-TM -极化键的配合物。这些不同的结合方案将促进不同的反应性和催化作用，这将相互补充和对比。合成各种TM-Al络合物将使我们能够评估直接键合的Al中心对杂环催化的影响范围，从不参与某些反应的旁观者配体到调节TM的电子性质的例子，与TM中心合作参与以促进底物活化