A Facile Route toward Ceric Silylamide [Ce{N(SiHMe2)2}4

Abstract

Treatment of the ate complex [Ce{N(SiHMe2)2}4Li(thf)] with neutral donor molecules (do) gave several solvent(do)‐separated ion‐pair complexes of the composition [Ce{N(SiHMe2)2}4][Li(do)n] (do = thf, pyridine, tmeda, dme, 12‐crown‐4). Their solid‐state structures have been analyzed by X‐ray diffraction and DRIFTS. Displacement of the [Li(do)n] entity, resulting in a solvent‐separated ion pair with a symmetric environment around the Ce(III) center, was also revealed in solution by 7Li NMR spectroscopy. The oxidation of [Ce{N(SiHMe2)2}4][Li(do)n] with 1,4‐benzoquinone to afford homoleptic ceric [Ce{N(SiHMe2)2}4] has been investigated and screened. Overall, the separated ion pairs [Ce{N(SiHMe2)2}4][Li(do)n] performed better than the intramolecular ate complex [Ce{N(SiHMe2)2}4Li(thf)], with pyridine as donor giving the best results.