Synthesis and structure of bismuth complexes [p-Tol4E]+3[Bi3I12]3–.HOCH2CH2OC2H5, E=P, Sb

Abstract

The interaction of equimolar amounts of tetra-p-tolylphosphonium and tetra-ptolylstybonium iodides with bismuth triiodide in 2-ethoxyethanol leads to formation of the complexes [p-Tol4E]+3[Bi3I12]3– ∙ HOCH2CH2OC2H5 E=P (I), Sb (II). X-ray diffraction analysis of compounds (I) and (II) has shown that in the cations of complexes I and II the coordination of phosphorus and antimony atoms is tetrahedral (angles equal: CPC 107.3(3)°–113.4(4)°(I), CSbC 105.4(3)°–113.7(3)° (II); bond lengths for P–C and Sb–C are 1.761(9)–1.815(7) Å and 2.085(8)–2.099(8) Å, respectively). In trinuclear anions [Bi3I12]3- the terminal fragments BiI3 (Bi–Iterm 2.8714(5)–2.9181(5) Å (I), 2.8867(5)–2.9248(6) Å (II)) are bonded to the central bismuth atom through six μ2-bridging iodine atoms (Bi-Ibr 3.0454(6)-3.3891(6) Å (I), 3.0595(4)–3.3694(6) Å (II)). Взаимодействием эквимолярных количеств иодидов тетра-п-толилфосфония и тетра-п-толилстибония с трииодидом висмута в 2-этоксиэтаноле получены комплексы [p-Tol4E]+3[Bi3I12]3–∙HOCH2CH2OC2H5 E=P (I), Sb (II). Проведен рентгеноструктурный анализ I и II. В катионах координация атомов фосфора и сурьмы тетраэдрическая (углы CPC 107.3(3)°–113.4(4)° (I), CSbC 105.4(3)°–113.7(3)° (II); связи P–C 1.761(9)-1.815(7) Å (I), Sb–C 2.085(8)–2.099(8) Å (II). В трехъядерных анионах [Bi3I12]3– концевые фрагменты BiI3 (Bi-Iтерм 2.8714(5)–2.9181(5) Å (I) 2.8867(5)–2.9248(6) Å (II)) связаны с центральным атомом висмута посредством шести μ2-мостиковых атомов иода (Bi–Iмост 3.0454(6)–3.3891(6) Å (I) 3.0595(4)–3.3694(6) Å (II)).