I Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Chem Commun (Camb). 2019 Oct 29;55(87):13031-13047. doi: 10.1039/c9cc05605j.
The synthesis and reactivity of uranium compounds supported by the tris-tert-butoxysiloxide ligand is surveyed. The multiple binding modes of the tert-butoxysiloxide ligand have proven very well suited to stabilize highly reactive homo- and heteropolymetallic complexes of uranium that have shown an unusual high reactivity towards small molecules such as CO2, CS2, chalcogens and azides. Moreover, these ligands have allowed the isolation of dinuclear nitride and oxide bridged complexes of uranium in various oxidation states. The ability of the tris-tert-butoxysiloxide ligands to trap alkali ions in these nitride or oxide complexes leads to unprecedented ligand based and metal based reduction and functionalization of N2, CO, CO2 and H2.
三(叔丁氧基)硅烷配体支撑的铀化合物的合成和反应性得到了调查。叔丁氧基硅烷配体的多种结合模式被证明非常适合稳定高反应性的同核和异核多金属铀配合物，这些配合物对小分子如 CO2、CS2、硫属元素和叠氮化物表现出异常高的反应活性。此外，这些配体还允许在各种氧化态下分离出双核氮化物和氧化物桥联的铀配合物。三(叔丁氧基)硅烷配体在这些氮化物或氧化物配合物中捕获碱金属离子的能力导致了前所未有的基于配体和基于金属的 N2、CO、CO2 和 H2 的还原和官能化。
