Synthesis and Structure of Phosphorus-Containing Complexes [Ph_4P]_2~+[Hg_4I_(10)]~(2-)and [Ph_4P]_2~+[BiI_5(Me_2S=O)]~(2-)

摘要

Complexes [Ph_4P]_2~+ [Hg_4I_(10)]~(2-)(I)and [Ph_4P]_2~+ [BiI_5(Me_2S=O)]~(2-)(II)are synthesized by the reactions of tetraphenylphosphonium Ph_4PI 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 cen-trosymmetric anion [Hg_4I_(10)]~(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.