CИНТЕЗ И СТРОЕНИЕ ГЕКСАХЛОРЦИРКОНАТОВ ТРИФЕНИЛБУТ-2-ЕНИЛ- И ТРИФЕНИЛМЕТОКСИМЕТИЛФОСФОНИЯ

Abstract

Triphenylbut-2-enyl- (1a) and triphenylmetoxymethylphosphonium (1b) hexachlorozir-conates have been synthesized by the reactions of zirconium tetrachloride with the triphenyl-alkylphosphonium chlorides in acetonitrile for the first time and characterized by the IR, NMR spectroscopy and X-ray analysis. The most intensive bands in IR spectra correspond to the valence vibrations of the CAr-H and the CAr-CAr bonds in the triphenylalkylphosphonium cations. The splitting of carbon atoms signals is observed due to the presence of 13C - 31P coupling. SSCC for carbon atoms directly connected with phosphorus are about 48-85 Hz. According to the X-Ray data, compound 1a crystallizes in the monoclinic crystal lattice (the P21/c space symmetry group). Hexachlorozirconate 1b forms the triclinic crystals belong to the P-1 space symmetry group. Crys-tals of compound 1a is characterized by the less dense molecular packing in the crystal lattice in comparison with compound 1b. Calculated densities for the structures 1a,b are 1.355 g/cm3 and 1.466 g/cm3, respectively. Structural organization of the complexes in crystals is caused by the for-mation of hydrogen bonds between chlorine atoms of the anion and hydrogens of phenyl and alkyl groups of the cations. The phosphorus atoms in the triphenylalkylphosphonium cations have dis-torted tetrahedral coordination (CPC 107.01(4)°-114.10(6)° for 1a, 107.38(9)°-112.06(7)° for 1b, the P-C bonds are 1.790(14)-1.865(14) Å for 1a, 1.7838(12)-1.8293(18) Å for 1b). In centrosym-metric octahedral anions [ZrCl6]2− (trans-ClZrCl 180°) the Zr-Cl distances are 2.4654(15)-2.4952(17) Å for 1a and 2.4641(14)-2.4711(12) Å for 1b.