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Titanium perchlorate is a molecular compound of titanium and perchlorate groups with formula Ti(ClO4)4. Anhydrous titanium perchlorate decomposes explosively at 130 °C and melts at 85 °C with a slight decomposition. It can sublime in a vacuum as low as 70 °C, and can form vapour at up to 120°. Titanium perchlorate is quite volatile. It has density 2.35. It decomposes to TiO2, ClO2 and dioxygen O2 Also TiO(ClO4)2 is formed during decomposition.[2]

Ti(ClO4)4 → TiO2 + 4ClO2 + 3O2 ΔH = +6 kcal/mol (25 kJ/mol).[2]

Properties

The Ti(ClO4)4 molecule has the perchlorate groups bidentately bonded to the titanium atom via two oxygen atoms.[2] So the molecule could also be called tetrakis(perchlorato-O,O')titanium(IV).[3]

In the solid form it forms clear coloured monoclinic crystals, with unit cell parameters a=12.451 b=7.814 c=12.826 Å α=108.13. Unit cell volume is 1186 Å3 at -100 °C. There are four molecules per unit cell.[1]

It reacts with petrolatum, nitromethane, acetonitrile, dimethylformamide, and over 25° with carbon tetrachloride.[2]

Titanyl perchlorate also exists in solvates with water, dimethyl sulfoxide, dioxane, pyridine-N-oxide and quinoline-N-oxide.[2]

Formation

Titanium perchlorate can be formed by reacting titanium tetrachloride with perchloric acid enriched in dichlorine heptoxide.[2] Another way uses titanium tetrachloride with dichlorine hexoxide. This forms a complex with Cl2O6 which when warmed to 55° in a vacuum, sublimes and can crystallise the pure anhydrous product from the vapour.[1]

Related

In the salt dicaesium hexaperchloratotitanate, Cs2Ti(ClO4)6 the perchlorate groups are monodentate, connected by one oxygen to titanium.[4]

Titanium perchlorate can also form complexes with other ligands bound to the titanium atom including binol,[5] and gluconic acid.[6]

A polymeric oxychlorperchlorato compound of titanium, Ti6O4Clx(ClO4)16−x, is made from excess TiCl4 and dichlorine hexoxide. This has a varying composition, and ranges from light to dark yellow.[7]

References

  1. ^ a b c Fourati, Mohieddine; Chaabouni, Moncef; Belin, Claude Henri; Charbonnel, Monique; Pascal, Jean Louis; Potier, Jacqueline (April 1986). "A strongly chelating bidentate perchlorate. New synthesis route and crystal structure determination of titanium(4+) perchlorate". Inorganic Chemistry. 25 (9): 1386–1390. doi:10.1021/ic00229a019.
  2. ^ a b c d e f Babaeva, V. P.; Rosolovskii, V. (1974). "Volatile titanium perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 23 (11): 2330–2334. doi:10.1007/BF00922105. ISSN 0568-5230.
  3. ^ Macintyre, Jane E. (1992). Dictionary of Inorganic Compounds. CRC Press. p. 2963. ISBN 9780412301209.
  4. ^ Babaeva, V. P.; Rosolovskii, V. Ya. (November 1975). "Production of cesium hexaperchloratotitanate by the reaction of titanium perchlorate with cesium perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 24 (11): 2278–2281. doi:10.1007/BF00921631.
  5. ^ Mikami, Koichi; Sawa, Eiji; Terada, Masahiro (January 1991). "Asymmetric catalysis by chiral titanium perchlorate for carbonyl-ene cyclization". Tetrahedron: Asymmetry. 2 (12): 1403–1412. doi:10.1016/S0957-4166(00)80036-1.
  6. ^ Guthrie, R. D. (1970). Carbohydrate Chemistry. Vol. 3. London: Royal Society of Chemistry. p. 144. ISBN 9780851860220.
  7. ^ Fourati, M.; Chaabouni, M.; Pascal, J.L.; Potter, J. (March 1986). "Synthesis and vibrational analysis of new anhydrous oxochloroperchlorato complexes of titanium IV". Journal of Molecular Structure. 143 (1–2): 147–150. Bibcode:1986JMoSt.143..147F. doi:10.1016/0022-2860(86)85225-5.
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