A Facile Route toward Ceric Silylamide [Ce{N(SiHMe2)2}4]. Issue 1 (6th November 2019)

• Record Type: Journal Article
• Authors: Bayer, Uwe; Bock, Lorenz; Maichle‐Mössmer, Cäcilia; Anwander, Reiner
• Is Part Of: European journal of inorganic chemistry. Issue 1(2020)
• Page Start: 101
• Page End: 106
• Publication Date: 2019-11-06
• Subjects: Cerium -- Redox chemistry -- Silylamides -- Solvent‐separated ion pairs; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201901023
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Treatment of the ate complex [Ce{N(SiHMe2 )2 }4 Li(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 7 Li 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 }4 Li(thf)], with pyridine as donor giving the best results. Abstract : Alkali‐metal separation in ate complex precursors via additional donor molecules ensures higher yields in the benzoquinone (bq)‐promoted oxidation aiming at ceric silylamide [Ce{N(SiHMe2 )2 }4 ].