Synthesis and characterization of volatile cerium(IV) hexafluoroisopropoxide complexes. Structure of [Hpmdien]₂[Ce{OCH(CF₃)₂}₆]

Abstract

The reaction between the cerium isopropoxide [Ce₂(OPrⁱ)₈(PrⁱOH)₂] and hexafluoroisopropyl alcohol (Hhfip) in THF at room temperature resulted in the formation of [Ce(hfip)₄(THF )₂(PrⁱOH)_x]. More stable compounds namely [Ce(hfip)₄(diglyme)], [Ce(hfip)₄(bipy)₂] and [Ce(hfip)₄(tmen)] were obtained if the alcoholysis was achieved in the presence of a Lewis base (diglyme = 2,5,8-trioxanonane, bipy = 2,2′-bipyridine, tmen = N,N,N ′,N ′-tetramethylethane-1,2-diamine). The use of N,N,N ′,N ″,N ″-pentamethyldiethylenetriamine (pmdien) afforded [Hpmdien]₂[Ce(hfip)₆] and [Ce(hfip)₃(OPrⁱ)(pmdien)]. All compounds were volatile and characterized by elemental analyses, FT-IR, ¹H and ¹⁹F NMR. The pmdien salt was also characterized by X-ray diffraction. The cerium atom is six-co-ordinated [Ce–O 2.183(5)–2.208(5) Å] with the CF₃ groups forming nearly a crown (Ce  · · ·  F 4.06–4.32 Å). The metallic anion [Ce(hfip)₆]^2– and the [Hpmdien]⁺ cations are associated by a short F  · · ·  C contact (3.15 Å). The interactions are retained in solution as evidenced by ¹H and ¹⁹F NMR.

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