Titanium perchlorate

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]

Titanium perchlorate
Identifiers
3D model (JSmol)
Properties
Ti(ClO4)4
Molar mass 445.65 g·mol−1
Appearance white crystals,
deliquescent
Density 2.49 g/cm3 (anhydrous)
Melting point 85 °C (185 °F; 358 K) (anhydrous) slight decomposition
Boiling point decomposition
high
Related compounds
Other anions
 Titanium nitrate
Other cations
 Zirconium perchlorate
Hafnium perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Ti(ClO4)4 → TiO2 + 4ClO2 + 3O2 ΔH=+6 kcal/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]

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. 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. 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. 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.
Compounds containing perchlorate group
HClO4 He
LiClO4 Be(ClO4)2 B(ClO
4)−
4
B(ClO4)3		 ROClO3 N(ClO4)3
NH4ClO4
NOClO4		 O FClO4 Ne
NaClO4 Mg(ClO4)2 Al(ClO4)3 Si P S ClO−
4
ClOClO3
Cl2O7		 Ar
KClO4 Ca(ClO4)2 Sc(ClO4)3 Ti(ClO4)4 VO(ClO4)3
VO2(ClO4)		 Cr(ClO4)3 Mn(ClO4)2 Fe(ClO4)3 Co(ClO4)2,
Co(ClO4)3		 Ni(ClO4)2 Cu(ClO4)2 Zn(ClO4)2 Ga(ClO4)3 Ge As Se Br Kr
RbClO4 Sr(ClO4)2 Y(ClO4)3 Zr(ClO4)4 Nb(ClO4)5 Mo Tc Ru Rh(ClO4)3 Pd(ClO4)2 AgClO4 Cd(ClO4)2 In(ClO4)3 Sn(ClO4)4 Sb TeO(ClO4)2 I Xe
CsClO4 Ba(ClO4)2   Hf(ClO4)4 Ta(ClO4)5 W Re Os Ir Pt Au Hg2(ClO4)2,
Hg(ClO4)2		 Tl(ClO4),
Tl(ClO4)3		 Pb(ClO4)2 Bi(ClO4)3 Po At Rn
FrClO4 Ra   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce(ClO4)x Pr Nd Pm Sm(ClO4)3 Eu(ClO4)3 Gd(ClO4)3 Tb(ClO4)3 Dy(ClO4)3 Ho(ClO4)3 Er(ClO4)3 Tm(ClO4)3 Yb(ClO4)3 Lu(ClO4)3
Ac Th(ClO4)4 Pa UO2(ClO4)2 Np Pu Am Cm Bk Cf Es Fm Md No Lr
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