Synthesis and structure of bismuth complexes [Ph₃MeP] ⁺₆ [BiI₃Br₃]³⁻[Bi₂I₆Br₃]³⁻ · H₂O₂, [Ph₃EtP] ⁺₃ [Bi₂I₉]³⁻, [Ph₃MeP] ⁺₃ [Bi₃I₁₂]³⁻, [Ph₃(iso-Pr)P] ⁺₃ [Bi₃I₁₂]³⁻ · 2Me₂C=O, and [Ph₄Bi] ⁺₃ [Bi₅I₁₈]³⁻

Abstract

A number of complexes with bismuth-containing anions, [Ph₃MeP] ⁺₆ [BiI₃Br₃]³⁻ [Bi₂I₆Br₃]³⁻ · H₂O₂ (I), [Ph₃EtP] ⁺₃ [Bi₂I₉]³⁻ (II), [Ph₃MeP] ⁺₃ [Bi₃I₁₂]³⁻ (III), [Ph₃(iso-Pr)P] ⁺₃ [Bi₃I₁₂]³⁻ · 2Me₂C=O (IV), and [Ph₄Bi] ⁺₃ [Bi₅I₁₈]³⁻ (V), were obtained by reactions of triphenylphosphonium halides and tetraphenylbismuth 3-carboxy-4-hydroxybenzenesulfonate with bismuth iodide. The central atom in the complex cations has a distorted tetrahedral coordination. In the mononuclear octahedral anion [BiI₃Br₃]³⁻, the bromine and iodine atoms are located on the opposite octahedron faces. The binuclear [Bi₂I₆Br₃]³⁻ anion contains three bridging iodine atoms and terminal BiI₃ and BiBr₃ fragments; in the centrosymmetrical [Bi₂I₉]³⁻ anion, the Bi-I bond lengths (2.933–3.360 Å) are comparable with similar bonds in I (2.935–3.257 Å). In the anion of complex III, each of terminal BiI₃ groups is linked to the central Bi atom by two μ₂- and one μ₃-iodine bridges (the BiBiBi angle is 101.54°). In the anions of complexes IV and V, the bismuth atoms of Bi₃ and Bi₅ groups occur on a straight line.