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

Abstract

Treatment of the ate complex [Ce{N(SiHMe 2 ) 2 } 4 Li(thf)] with neutral donor molecules (do) gave several solvent(do)‐separated ion‐pair complexes of the composition [Ce{N(SiHMe 2 ) 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 7 Li NMR spectroscopy. The oxidation of [Ce{N(SiHMe 2 ) 2 } 4 ][Li(do) n ] with 1,4‐benzoquinone to afford homoleptic ceric [Ce{N(SiHMe 2 ) 2 } 4 ] has been investigated and screened. Overall, the separated ion pairs [Ce{N(SiHMe 2 ) 2 } 4 ][Li(do) n ] performed better than the intramolecular ate complex [Ce{N(SiHMe 2 ) 2 } 4 Li(thf)], with pyridine as donor giving the best results.