Zirconium Complexes [Ph3PR] sub arrange=stack 2 sup arrange= stack +[ZrCl6]2-, R = Et, CH2Ph, CH2C(O)OMe: Synthesis and Structure

The complexes [Ph3PR]<[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)degrees-110.84(8)degrees (I), 106.91(8)degrees 112.21(8)degrees (II), and 107.26(9)degrees-112.83(9)degrees (III), and the P-C bond lengths are 1.793(2)-1.803(2) angstrom (I), 1.791(2)-1.824(2) angstrom (II), and 1.784(2)-1.811(2) angstrom (III). The Zr-Cl distances in the centrosymmetric octahedral anions [ZrCl6](2-) of complex I are 2.4625(11)-2.4634(11) angstrom. The octahedral configuration of anions in complexes II and III is distorted: the trans-ClZrCl angles are 176.80(2)degrees, 177.12(2)degrees, 179.80(2)degrees (II) and 175.53(3)degrees, 175.97(2)degrees, 177.75(2)degrees (III), and the Zr-Cl bonds are 2.4489(11)-2.4953(15) angstrom (II) and 2.4510(8)-2.4864(9) angstrom (III).