[Na-15-Krone-5]2[ZrF2Cl4] und (PPh4)2[ZrCl6] · 2 CH2Cl2; Synthesen, IR-Spektren und Kristallstrukturen / [Na-15-Crown-5]2[ZrF2Cl4] and (PPh4)2[ZrCl6] · 2 CH2Cl2; Syntheses, IR Spectra, and Crystal Structures

Abstract

[Na-15-crown-5]2[ZrF2Cl4] has been prepared by the reaction of the amidinato complex [Ph—C(NSiMe3)2ZrCl3]2 with sodium fluoride in acetonitrile suspension, as well as by the reaction of ZrCl4 in acetonitrile, both in the presence of 15-crown-5. On an analogous route (PPh4)2[ZrCl6] · 2 CH2Cl2 has been prepared by the reaction of [Ph—C(NSiMe3)2ZrCl3]2 with PPh4Cl in CH2Cl2 solution, as well as by the reaction of ZrCl4 with PPh4Cl in CH2Cl2. The compounds are characterized by their IR spectra and by crystal structure determinations. [Na-15-crown-5]2[ZrF2Cl4]: Space group Ρ21/a, Z = 4, 6589 observed independent reflexions, R = 0.069. Lattice dimensions at 20°C: a = 1705.0(9), b = 1092.4(6), c = 1906.5(10) pm, β = 113.14(3)°. [Na-15-crown-5]2[ZrF2Cl4] forms ion triples, in which both sodium ions are sevencoordinate by five oxygen atoms of the crown ether molecules, as well as by a fluorine and a chlorine atom of the cis-[ZrF2Cl4]2- unit. (PPh4)2[ZrCl6] · 2 CH2Cl2: Space group P1̄, Z = 1, 4831 observed independent reflexions, R = 0.041. Lattice dimensions at 20°C: a = 1030.1(5), b = 1124.8(6), c = 1245.6(6) pm, α = 70.81(3), β = 80.61(4), γ = 80.39(4)°. The compound has an ionic structure with ZrCl6 2- ions of symmetry Ci.