Zirconium perchlorate reacts irreversibly with most organic compounds but is inert towards carbon tetrachloride, chloroformide. With benzene at -10°C, crystals of Zr(ClO4)4•C6H6 are deposited.
Solid zirconium perchlorate undergoes a phase transition around 45 °C before melting between 95.5 and 96.0 °C. Thermolysis near 120 °C gives zirconyl perchlorate. Further heating around 290°C gives form zirconia and chlorine oxides.[1]
Structure
In the gas phase the Zr(ClO4)4 molecule has a D4 symmetry with eightfold square antiprism oxygen coordination. Each perchorate group is bidentate. The chlorine atoms are in a tetrahedral arrangement around the central zirconium.[3]
In the solid phase, Zr(ClO4)4 crystals are monoclinic with a=12.899, b=13.188, c=7.937 Å, β=107.91°. There are four molecules per unit cell.[4]
Salts of perchloratozirconates and hexaperchloratozirconates have been claimed including the caesium perchloratozirconates CsZr(ClO4)5, Cs2Zr(ClO4)6, and Cs4Zr(ClO4)8.[5][6]. The very close analogues of zirconium perchlorate are zirconium pertechnetates and perrhenates, however, unlike it, they crystallize from an aqueous solution in the form of dimers of the composition [Zr2(MO4)6(μ-OH)2(H2O)6]..3H2O (M = Tc and Re).[7]
Zirconyl perchlorates have been claimed in older literature.[8]
References
^ abcBabaeva, V. N.; Rosolovskii, V. Ya. (March 1977). "Anhydrous zirconium perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 26 (3): 445–449. doi:10.1007/BF01179439.
^Lapshina, S.B.; Ermolaeva, L.I.; Girichev, G.V.; Spiridonov, V.P.; Golubinskii, A.V. (1999). "Electron Diffraction Study of the Molecular Structure of Zirconium Perchlorate in the Gas Phase". Russian Journal of Inorganic Chemistry. 44 (4): 485–488.
^Krivtsov, N. V.; Babaeva, V. P.; Rosolovskii, V. Ya. (April 1990). "A thermochemical study of cesium and nitrile perchloratozirconates". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 39 (4): 817–820. doi:10.1007/BF00960355. S2CID96641367.
^Babaeva, V. P.; Rosolovski, V. Ya. (1978). "Synthesis and Properties of cesium perchloratozirconates". Zhurnal Neorganicheskoj Khimii. 23 (4): 955–959.
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