The development of multi-metallic low oxidation state main-group compounds

催化化学过程是现代合成化学的基石，在大规模生产商品化学品、药物开发和材料制造等方面都有应用。许多均相催化过程是由昂贵的贵金属介导的，这些贵金属往往供应有限，最著名的例子可能是基于第10族过渡金属铂和钯的。近年来，人们的注意力转向寻找过渡金属的丰富和更具成本效益的替代品，大多数早期的主族元素都符合这一特征。然而，由于最终控制其反应活性的电子构型的显著差异，从过渡金属络合物到主族元素的化学反应性的转换远非微不足道。过渡金属很容易以多种氧化态存在，氧化态之间的相互转化驱动着氧化还原(还原消除，氧化加成)催化--这是建立和断裂化学键的主要手段之一。主族元素通常有一种热力学上有利的氧化态，这排除了简单的氧化还原化学。近年来，在热力学上不受欢迎的“低氧化态”中分离主族元素方面取得了进展，氧化反应活性相对较好。然而，可逆反应(即氧化加成和还原消除)的例子很少，早期主要基团中的氧化还原催化只在单一情况下推断。因此，氧化还原活性主族体系的开发是合成无机化学的主要目标，这最终将为更可持续和更具成本效益的化学过程奠定基础。该项目将发展早期主族元素的氧化还原化学，创造前所未有的低氧化态金属络合物，能够氧化活化和还原消除工业上相关的小分子碎片。拟议的研究重点是开发多金属低氧化态络合物--含有两种或两种以上富含电子的金属的化合物。这些多金属体系将具有协同效应和合作效应，因为金属之间的相互作用和金属位置的互补活性使相互接近的金属受益于增强的反应性。了解这些化合物的基本成键结构和基本反应活性对于主族化合物氧化还原化学的继续发展至关重要。最终目标是创造一系列多金属络合物，从化学计量反应性转化为催化作用。

Catalytic chemical processes are the cornerstone of modern synthetic chemistry, with application in, for example, the large scale production of commodity chemicals, drug development and materials manufacturing. Many homogeneous catalytic processes are mediated by expensive precious metals which are often in limited supply, with perhaps the most famous examples based on the group 10 transition metals platinum and palladium. Attention in recent years has turned to finding Earth abundant and more cost effective alternatives to transition metals, with most early main-group elements fitting this profile. However, translation of chemical reactivity from transition metal complexes to main-group elements is far from trivial due to significant differences in the electronic configuration that ultimately controls their reactivity. Transition metals readily exist in multiple oxidation states, with interconversion between oxidation states driving redox (reductive elimination, oxidative addition) catalysis - one of the primary means of making and breaking chemical bonds. Main-group elements typically have one thermodynamically favoured oxidation state, which precludes facile redox chemistry. Recent years have seen advances in the isolation of main-group elements in thermodynamically unfavoured 'low oxidation states', with oxidative reactivity relatively well established. However, examples of reversible reactions (i.e. oxidative addition AND reductive elimination) are few and far between, with redox catalysis in the early main-group only inferred in a single case. The development of redox active main-group systems is therefore a major target in synthetic inorganic chemistry, which will ultimately lay the foundation for more sustainable and cost-effective chemical processes. This project will develop the redox chemistry of early main-group elements, creating unprecedented new low oxidation state metal complexes capable of oxidatively activating and reductively eliminating small, industrially relevant molecular fragments. The proposed research focuses on the development of multi-metallic low oxidation state complexes - compounds that contain two or more metals rich in electrons. These multi-metallic systems will have synergistic and cooperative effects, with metals in close proximity to one another benefiting from enhanced reactivity through metal orbital interactions and the complementary activity of metal sites. Understanding the underlying bonding structure and fundamental reactivity of these compounds is crucial for the continued development of redox chemistry in main-group compounds. The ultimate goal is to create a range of multi-metallic complexes from which stoichiometric reactivity can be translated to catalysis.