Hypervalent diorganoantimony(iii) fluorides via diorganoantimony(iii) cations – a general method of synthesis

Abstract

Novel diorganoantimony(III) fluorides containing ligands with pendant arms, R₂SbF (5), (R)PhSbF (6) [R = 2-(2′,6′-ⁱPr₂C₆H₃NCH)C₆H₄], R′′₂SbF (7) and (R′′)PhSbF (8) [R′′ = 2-(Me₂NCH₂)C₆H₄], were prepared via the ionic derivatives [R₂Sb]⁺[PF₆]⁻ (1), [(R)PhSb]⁺[PF₆]⁻ (2), [R′′₂Sb]⁺[SbF₆]⁻ (4) and [(R′′)PhSb]⁺[SbF₆]⁻ (obtained in situ) by treatment with [Bu₄N]F·3H₂O. The ionic species used as starting materials as well as [R′₂Sb]⁺[PF₆]⁻ (3) [R′ = 2-(2′,4′,6′-Me₃C₆H₂NCH)C₆H₄] were obtained from the corresponding bromides or chlorides and Tl[PF₆] or Ag[SbF₆]. The compounds were investigated by multinuclear NMR spectroscopy in solution, MS and IR spectroscopy in the solid state. The molecular structures of the ionic species 1·2CH₂Cl₂ and 3·2CHCl₃ as well as of the fluorides 5–8 were determined by single-crystal X-ray diffraction.