Synthesis and Structure of Phosphorus-Containing Complexes [Ph4P] 2 + [Hg4I10]2− and [Ph4P] 2 + [BiI5(Me2S=O)]2−

Abstract

Complexes [Ph4P]2+[Hg4I10]2− (I) and [[Ph4P]2+[BiI5(Me2S=O)]2− (II) are synthesized by the reactions of tetraphenylphosphonium Ph4PI with mercury diiodide in acetone and with bismuth triiodide in dimethyl sulfoxide, respectively. According to X-ray diffraction analysis, structural units of these complexes are tetraphenylphosphonium cations and tetra- and mononuclear anions, respectively. The phosphorus atoms in the tetraphenylphosphonium cations have a distorted tetrahedral coordination. In the central fragment of the centrosymmetric anion [Hg4I10]2−, the distances between the terminal mercury atoms and iodine atoms are 3.503(2) A. The mercury atoms in the central and terminal fragments of compound I have distorted tetrahedral and trigonal coordinations, respectively. The bismuth atom in the mononuclear octahedral anion of complex II contains a dimethyl sulfoxide molecule along with five iodine atoms in the coordination sphere.