Zirconium Complexes [Ph3PR]2+[ZrCl6]2–, R = Et, CH2Ph, CH2C(O)OMe: Synthesis and Structure

Abstract

The complexes [Ph₃PR]₂⁺[ZrCl₆]^2–, R = Et (I), CH₂Ph (II) (1: 1 solvate with acetonitrile), and CH₂C(O)OMe (III) have been synthesized by the reaction between zirconium tetrachloride and triphenylorganyl phosphonium chlorides in acetonitrile and structurally characterized. The phosphorus atoms in triphenylorganyl phosphonium cations have a distorted tetrahedral coordination: the CPC angles are 108.29(9)°–110.84(8)° (I), 106.91(8)°—112.21(8)° (II), and 107.26(9)°–112.83(9)° (III), and the P–C bond lengths are 1.793(2)–1.803(2) Å (I), 1.791(2)–1.824(2) Å (II), and 1.784(2)–1.811(2) Å (III). The Zr–Cl distances in the centrosymmetric octahedral anions [ZrCl₆]^2– of complex I are 2.4625(11)–2.4634(11) Å. The octahedral configuration of anions in complexes II and III is distorted: the trans-ClZrCl angles are 176.80(2)°, 177.12(2)°, 179.80(2)° (II) and 175.53(3)°, 175.97(2)°, 177.75(2)° (III), and the Zr–Cl bonds are 2.4489(11)–2.4953(15) Å (II) and 2.4510(8)−2.4864(9) Å (III).