Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

Abstract

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.