Synthesis and Structure of (4-Fluoro-benzyl)triphenylphosphonium Hexachlorozirconate [Ph3PCH2C6H4F-4][ZrCl6].
Keywords:
zirconium tetrachloride, (4-fluorobenzyl)triphenylphosphonium chloride, (4 fluorobenzyl)triphenylphosphonium hexachlorozirconate, addition reactionAbstract
(4-Fluorobenzyl)triphenylphosphonium hexachlorozirconate [Ph3PCH2C6H4F-4]2[ZrCl6]2– (1) have been synthesized via the reaction of (4 fluorobenzyl)triphenyl-phosphoniun chloride with zirconium tetrachloride in acetonitrile solution. The structure of the compound was characterized by IR, 1Н, 13С{1Н} and 19F{1Н} NMR-spectroscopy, elemental analysis, and single-crystal X-ray diffraction. According to the X-ray data the crystals of complex 1 consist of two types of tetrahedral (4-fluorobenzyl)triphenylphosphoniun cations (the СРС angles are 99.44(13)114.94(12), the PC distances are 1.706(2)1.935(3) Å) and octahedral anions [ZrCl6]2– (the СlZrCl trans-angles are 177.35(3)178.62(3), the ZrCl distances are 2.4308(9)2.5350(11) Å). The structure of complex 1 is formed due to weak hydrogen bonds between cations and anions. The IR spectrum of complex 1 contains an intense band of stretching vibrations of the F–CAr bond at 997 cm–1, a band of vibrations of the P–СAr bonds at 1439 cm–1, and bands of bending and stretching vibrations of C–H at 743 and 3059, 2912 cm–1. In the 31Р NMR spectrum of complex 1 the characteristic signal is a doublet due to long-range interaction at the fluorine atom (J = 8.8 Hz). All signals of carbon atoms in the 13C NMR spectrum, due to direct and long-range interactions with fluorine and phosphorus atoms, are observed in the form of doublets and doublet-doublets.References
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