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Triphenylbut-2-enyl- (1a) and triphenylmetoxymethylphosphonium (1b) hexachlorozirconates have been synthesized by the reactions of zirconium tetrachloride with the triphenylalkylphosphonium 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 СAr-СAr 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. Crystals 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/сm3, respectively. Structural organization of the complexes in crystals is caused by the formation 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 distorted tetrahedral coordination (CPC 107.01(4)°-114.10(6)°  for 1а, 107.38(9)°-112.06(7)° for 1b, the P-С bonds are 1.790(14)-1.865(14) Å for 1а, 1.7838(12)-1.8293(18) Å for 1b). In centrosymmetric octahedral anions [ZrCl6]2− (trans-ClZrCl 180°) the Zr-Cl distances are 2.4654(15)-2.4952(17) Å for 1а and 2.4641(14)-2.4711(12) Å for 1b.

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