Abstract
The 6-membered 3,5-bis(dimethylsilyl)-2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinan-1-ido ligand (dhts) was accessed in the potassium dimer [K(dhts)(thf)]2 (1thf), when treating KH with excess HN(SiHMe2)2 in the presence of THF. 1thf engaged in salt metathesis with CeCl3(thf)1.05 in THF, giving Ce(dhts)3(thf) (2thf). An attempted metathesis reaction in toluene failed, leading only to the recovery of 1thf. Attempts at generating potassium-ate complex {KCe(dhts)4} from salt metathesis between CeCl3(thf)1.05 and four equivalents of 1thf in THF, followed by crystallisation from toluene, resulted in the formation of both 2thf and [K(dhts)(toluene)]2 (1tol). Oxidation of 2thf with trityl chloride led to the isolation of the metastable tetravalent heteroleptic cerium complex Ce(dhts)3Cl (3), characterised by both 1H NMR spectroscopy and X-ray crystallography. Compound 3 is a new addition to a prominent class of cerium(IV) silylamides, and an understudied class of triazatrisilinanides.