Synthesis and derivatisation of ceric tris(tert-butoxy)siloxides

Chem Commun (Camb). 2017 Nov 2;53(88):12044-12047. doi: 10.1039/c7cc06499c.

Abstract

Metathesis reactions involving cerium(iv) complexes are generally hampered by a high tendency for reduction to the favoured trivalent state and a preference for ligand redistribution. Heteroleptic ceric Ce[OSi(OtBu)3]3Cl(thf) is easily obtained from the oxidation of Ce[OSi(OtBu)3]3(thf)2 with trityl chloride, while the absence of thf triggers formation of homoleptic Ce[OSi(OtBu)3]4. Ce[OSi(OtBu)3]3Cl(thf) engages in salt metathesis reactions with the alkali metal alkoxides KOCH3 and KOtBu, forming Ce[OSi(OtBu)3]3(OR)(thf)x, but experiences an extensive reductive ligand redistribution with the methylating agent ZnMe2.