Mixed triorganobismuthines RAr2Bi [Ar = C6F5, 2,4,6-(C6F5)3C6H2] and hypervalent racemic Bi-chiral diorganobismuth(iii) bromides RArBiBr (Ar = C6F5, Mes, Ph) with the ligand R = 2-(Me2NCH2)C6H4. Influences of the organic substituent

Abstract

Triorganobismuthines R(C₆F₅)₂Bi (1) and R[2,4,6-(C₆F₅)₃C₆H₂]₂Bi (2) [R = 2-(Me₂NCH₂)C₆H₄] were synthesized by reaction of RBiBr₂ with C₆F₅MgBr and 2,4,6-(C₆F₅)₃C₆H₂Li, respectively, in a 1 : 2 molar ratio. The Bi-chiral bromides R(C₆F₅)BiBr (3), R(Mes)BiBr (4), and R(Ph)BiBr (5) were obtained from RBiBr₂ and C₆F₅MgBr, MesMgBr or PhMgBr, or from PhBiBr₂ and RLi, in a 1 : 1 molar ratio. The molecular structures of 1–5 were determined by single-crystal X-ray diffraction and are discussed taking into account the chirality of the species. Supramolecular aspects in the solid state are presented. The solution behaviour of the title compounds, including dynamic aspects, are discussed on the basis of multinuclear (¹H, ¹³C, ¹⁹F) NMR spectroscopy.