SYNTHESIS AND STRUCTURE OF ZIRCONIUM [Ph<sub>3</sub>PCH=CHMe]<sub>2</sub>[ZrCl<sub>6</sub>] AND HAFNIUM [Ph<sub>3</sub>PCH<sub>2</sub>C(O)Me]<sub>2</sub>[HfCl<sub>6</sub>] COMPLEXES
The interaction of zirconium (IV) chloride and hafnium (IV) cloride with tetraorganylphosphonium chlorides in solutions of acetonitrile synthesized the following complexes: [Ph3PCH=CHCH3][ZrCl6] (1), [Ph3PCH2C(O)CH3][HfCl6] (2). The structures 1 and 2 were determined by XRDA and IR. The X-ray diffraction patterns of crystals 1 and 2 were obtained at 293 K on an automatic diffractometer D8 Quest Broker (MoK α radiation, λ = 0.71073 Å, graphite monochromator) the phosphorus atoms of complexes 1 and 2 have a distorted tetrahedral configuration in the cations. [C42H40P2Cl6Zr (1), M = 910.60; the triclinic syngony, the symmetry group P ; cell parameters: a = 10.189(8), b = 14.428(7), c = 15.229(8) Å; a = 83.31(2) degrees, β = 73.77(3) degrees, g = 87.75(3) degrees; V = 2135(2) Å3; the crystal size is 0.72 × 0.36 × 0.3 mm; intervals of reflection indexes -12 ≤ h ≤ 12, -18 ≤ k ≤ 18, -19 ≤ l ≤ 19; total reflections 36133; independent disclosures 7367; R int = 0.0326; GOOF = 1.180; R 1 = 0.0907; w R 2 = 0.2675; residual electron density -0.91/ 0.827 e/Å3, C42H40P2Cl6O1Hf (2), M = 1029.87; the triclinic syngony, the symmetry group P ; cell parameters: a = 10.323(3), b = 10.721(3), c = 11.122(3) Å; a = 67.634(13) degrees, β = 78.219(17) degrees, g = 73.041(14) degrees; V = 1082.7(5) Å3; the crystal size is 0.57 × 0.39 × 0.22 mm; intervals of reflection indexes -19 ≤ h ≤ 19, -20 ≤ k ≤ 20, -21 ≤ l ≤ 21; total reflections 118390; independent disclosures 16166; R int = 0.0486; GOOF 1.009; R 1 = 0.0447; w R 2 = 0.0772; residual electron density -1,013/0,910 e/Å3]. The СРС valence angles are 107.95(16)°-110.94(15)° and 106.72(17)°-113.51(17)° for 1, 105.85(15)°-110.97(15)° for 2, distance P-С 1.771(6)-1.801(6) Å и 1.781(6)-1.801(6) Å in 1; 1.790(2)-1.821(2) Å in 2. In octahedral anions [ZrCl6]2- and [HfCl6]2- trans-angles ClZrCl and ClHfCl equal 180.0º, distance 2.462(3)-2.476(3) Å и 2.462(2)- 2.468(2) Å in a crystal solvate in 1, 2.4513(10)-2.462(2) Å in 2. Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (No. 1913593 for 1, 1919938 for 2, deposit@ccdc.cam.ac.uk; http://www.ccdc. cam.ac.uk).