Titanium perchlorate

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Titanium perchlorate
Ti(ClO4)4.png
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/4ClHO4.Ti/c4*2-1(3,4)5;/h4*(H,2,3,4,5);/q;;;;+4/p-4
    Key: SOCDLWOJPVKBHF-UHFFFAOYSA-J
  • [Ti](O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)O[Cl](=O)(=O)=O
Properties
Ti(ClO4)4
Molar mass 445.65 g·mol−1
Appearancewhite 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).

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]

Contents

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]

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]

Related Research Articles

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as “tickle” or “tickle 4”, as a phonetic representation of the symbols of its molecular formula.

<span class="mw-page-title-main">Dichlorine heptoxide</span> Chemical compound

Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentoxide:

<span class="mw-page-title-main">Dichlorine monoxide</span> Chemical compound

Dichlorine monoxide is an inorganic compound with the molecular formula Cl2O. It was first synthesised in 1834 by Antoine Jérôme Balard, who along with Gay-Lussac also determined its composition. In older literature it is often referred to as chlorine monoxide, which can be a source of confusion as that name now refers to the ClO radical.

<span class="mw-page-title-main">Selenium tetrachloride</span> Chemical compound

Selenium tetrachloride is the inorganic compound composed with the formula SeCl4. This compound exists as yellow to white volatile solid. It is one of two commonly available selenium chlorides, the other example being selenium monochloride, Se2Cl2. SeCl4 is used in the synthesis of other selenium compounds.

<span class="mw-page-title-main">Dichlorine hexoxide</span> Chemical compound

Dichlorine hexoxide is the chemical compound with the molecular formula Cl
2
O
6
, which is correct for its gaseous state. However, in liquid or solid form, this chlorine oxide ionizes into the dark red ionic compound chloryl perchlorate [ClO
2
]+
[ClO
4
]
, which may be thought of as the mixed anhydride of chloric and perchloric acids.

<span class="mw-page-title-main">Chlorine perchlorate</span> Chemical compound

Chlorine perchlorate is a chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula ClOClO3. It is produced by the photodimerization of chlorine dioxide (ClO2) at room temperature by 436 nm ultraviolet light:

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

Barium perchlorate is a powerful oxidizing agent, with the formula Ba(ClO4)2. It is used in the pyrotechnic industry.

Chlorine tetroxide is an unstable chlorine oxide with the chemical formula ClO4.

Perchloratoborate is an anion of the form [B(ClO4)4]. It can form partly stable solid salts with heavy alkali metals. They are more stable than nitratoborate salts. K[B(ClO4)4] decomposes at 35 °C, Rb[B(ClO4)4] is stable to 50 °C, and Cs[B(ClO4)4] can exist up to 80 °C.

<span class="mw-page-title-main">Titanium(IV) nitrate</span> Chemical compound

Titanium nitrate is the inorganic compound with formula Ti(NO3)4. It is a colorless, diamagnetic solid that sublimes readily. It is an unusual example of a volatile binary transition metal nitrate. Ill defined species called titanium nitrate are produced upon dissolution of titanium or its oxides in nitric acid.

<span class="mw-page-title-main">Vanadyl perchlorate</span> Chemical compound

Vanadyl perchlorate or vanadyl triperchlorate is a golden yellow coloured liquid or crystalline compound of vanadium, oxygen and perchlorate group. The substance consists of molecules covalently bound and is quite volatile; it ignites organic solvents on contact and explodes at temperatures above 80 °C.

Zirconium perchlorate is a molecular substance containing zirconium and perchlorate groups with formula Zr(ClO4)4. Zr(ClO4)4 is a volatile crystalline product. It can be formed by reacting zirconium tetrachloride with dry perchloric acid at liquid nitrogen temperatures. Zr(ClO4)4 sublimes slowly in a vacuum at 70°C showing that the molecule is covalently bound rather than being ionic. The reaction also forms some zirconyl perchlorate (or zirconium oxyperchlorate) ZrO(ClO4)2 as even apparently pure perchloric acid is in equilibrium with dichlorine heptoxide, hydronium ions and perchlorate ions. This side product can be minimised by adding more dichlorine heptoxide or doing the reaction as cold as possible.

<span class="mw-page-title-main">Thorium(IV) nitrate</span> Chemical compound

Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.

Samarium(III) perchlorate is an inorganic compound with the chemical formula Sm(ClO4)3.

Chloryl tetraperchloratoaurate is an inorganic chemical compound with the formula ClO2Au(ClO4)4 consisting of the chloryl cation and a tetraperchloratoaurate anion. It is an orange solid that readily hydrolyzes in air.

<span class="mw-page-title-main">Nitrosyl perchlorate</span> Chemical compound

Nitrosyl perchlorate is the inorganic compound with the formula NO(ClO4). A hygroscopic white solid, it is the salt of the nitrosonium cation with the perchlorate anion. It is an oxidant and strong electrophile, but has fallen out of use with the availability of the closely related salt nitrosonium tetrafluoroborate NO(BF4).

Niobium perchlorate is a chemical compound with the formula Nb(ClO4)5. It is a hygroscopic, white crystalline solid that readily reacts with moist air or water to produce niobium(V) oxide.

References

  1. 1 2 3 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. 1 2 3 4 5 6 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.