Shedding light on main group organometallic chemistry

可见光作为一种清洁、选择性但又强大的能源的使用促进了合成方法的发展，否则通过热反应是无法获得的。照射在有机金属中间体上的光能够产生自由基中间体以及基态下无法达到的反应模式。然而，这项技术仍然以过渡金属(TM)及其容易与底物配位和在氧化态之间旋转为主。然而，它们不断上涨的成本、有限的供应和碳足迹(例如，Rh：GB 48,200/mol，0.001ppm，35,100 kg CO2/kg)促使化学家们专注于将这些关键特性注入d区块以外的更丰富和更无害的元素中。有趣的是，关于有机金属主族(MG)化合物的光敏性的零星例子已经被报道。已知低价态铟(In；GB 0.07/mol，0.052ppm，102 kg CO2/kg)和铝(Al；GB 0.07/mol，84,149 ppm，8.2 kg CO2/kg)在光照射下氧化加成几个键(H-H，H-Cl)，而基于锑的有机金属化合物(Sb；GB 1.5/mol，0.2ppm，13 kg CO2/kg)表现出光敏化作用，增强了它们对小分子活化的反应活性，并允许Sb-C键的均质断裂。这些特征是获得具有潜在应用于有机合成的活性中间体和自由基物种的关键。在这些特性的鼓舞下，这项跨学科的建议将专注于设计独特的双亲低价有机金属主族化合物，并测试它们对SMA的反应活性，如氢、氮和各种C-X键。我们将重点研究它们的关键电子性质(DFT与Rachel Creso-Otero博士合作)以及它们在光照射下对SMA的反应性，目的是模拟TM的可见光诱导过程。该项目将为基于丰富的P-块元素的催化光辅助合成工艺铺平道路，从而应对社会、学术和工业方面的全球挑战。

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.