Shedding light on main group organometallic chemistry

可见光作为一种清洁、选择性和强大的能源的使用，促进了合成方法的发展，否则通过热反应性手段是无法实现的。照射在有机金属中间体上的光使自由基中间体的产生以及基态无法达到的反应模式成为可能。然而，该技术仍然以过渡金属（TM）为主，它们易于配合衬底并在氧化态之间旋转。然而，它们不断上涨的成本、有限的供应和碳足迹（例如，Rh: 48200英镑/摩尔、0.001ppm、35100千克二氧化碳/千克）促使化学家们专注于将这些关键特性注入到d区以外更丰富、更良性的元素中。有趣的是，关于有机金属主基团（MG）化合物的光敏性，已有零星的报道。已知第13族相邻的铟（In； 0.07英镑/mol， 0.052ppm， 102千克二氧化碳/kg）和铝（Al； 0.07英镑/mol， 84,149 ppm， 8.2千克二氧化碳/kg）在光照射下会氧化增加几个键（H-H, H-Cl），而基于锑的有机金属第15族化合物（Sb； 1.5英镑/mol， 0.2ppm， 13千克二氧化碳/kg）表现出光敏性，增强了它们对小分子活化的反应性，并允许Sb- c键的均匀裂解。这些特征是获得活性中间体和自由基的关键，这些中间体和自由基具有应用于有机合成的潜力。在这些特性的鼓励下，这个跨学科的提案将专注于设计独特的两亲性低价有机金属主基团化合物，并测试它们对SMA的反应性，如氢、氮和各种C-X键。我们将重点研究它们的关键电子特性（与Rachel Crespo-Otero博士合作）和它们在光辐射下对SMA的反应性，目的是模拟已经建立的可见光诱导TM过程。该项目将为基于丰富p块元素的催化光辅助合成工艺铺平道路，从而解决社会，学术和工业兴趣的全球挑战。

The use of visible light as a clean, selective and yet powerful energy source has contributed to the development of synthetic methodologies otherwise inaccessible by means of thermal reactivity. Light irradiated on organometallic intermediates enables the generation of radical intermediates as well as reactivity modes that are unreachable in the ground state. This technology, however, is still dominated by transition metals (TM) and their ease to coordinate substrates and revolve between oxidation states. Yet, their rising cost, limited supply and carbon footprint (e.g., Rh: £48,200/mol, 0.001ppm, 35,100kg CO2/kg) urge chemists to focus on infusing these key properties to more abundant and benign elements beyond the d-block. Interestingly, scattered examples on the light sensitivity of organometallic main group (MG) compounds have been reported. Group 13 neighbours Indium (In; £0.07/mol, 0.052ppm, 102 kg CO2/kg) and Aluminium (Al; £0.07/mol, 84,149 ppm, 8.2kg CO2/kg) in low-valent states are known to oxidatively add to several bonds (H-H, H-Cl) under light irradiation, while organometallic group 15 compounds based on antimony (Sb; £1.5/mol, 0.2ppm, 13kg CO2/kg) exhibit photosensitisation, enhancing their reactivity towards small molecule activation and allowing homolytic cleavage of Sb-C bonds. These features are key to access reactive intermediates and radical species holding the potential to be applied to organic synthesis. Encouraged by these attributes, this interdisciplinary proposal will focus on the design of unique ambiphilic low-valent organometallic main group compounds and test their reactivity towards SMA, such as hydrogen, nitrogen and a variety of C-X bonds. We will focus on studying their key electronic properties (DFT in collaboration with Dr Rachel Crespo-Otero) and their reactivity towards SMA under light irradiation, with the aim of mimicking well-established visible-light-induced processes for TM. This project will pave the way towards catalytic light-assisted synthetic processes based on abundant p-block elements, thus tackling global challenges of social, academic, and industrial interest.