Amidinate stabilized cerium(IV) halide chemistry: synthesis and reactivity

We present an isostructural series of cerium(IV) amidinate complexes with halide co-ligands ranging from fluoride to iodide. Different routes are presented to access these valuable species, including the use of various oxidants such as the trichloride salt NMe 3 EtCl 3 or the tribromide salt NPh 3 MeBr 3 . In addition, we present the syntheses of rare triflate and cationic cerium(IV) complexes and first insights into the salt metathesis reactivity using (thio-)cyanates and azides are given. The synthesis of fluoride, chloride, bromide, iodide and triflate complexes of cerium(IV) supported by amidinate ligands is reported. The study shows versatile strategies to access these highly interesting species, discusses the structural properties of the complexes and shows their utility and limitations in salt metathesis reactions, as well as their UV–Vis spectroscopic properties. • Synthesis of a (pseudo-)halide series of cerium(IV) amidinate complexes. • Synthesis of cationic cerium(IV) complexes. • Structural characterization of a rare cerium(IV) triflate.