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.

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 ((1)H, (13)C, (19)F) NMR spectroscopy.