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Titanium perchlorate

Titanium perchlorate, or more precisely titanium(IV) perchlorate, is a molecular compound of titanium and perchlorate groups with formula Ti(ClO<sub>4</sub>)<sub>4</sub>. Anhydrous titanium perchlorate decomposes explosively at 130&nbsp;°C and melts at 85&nbsp;°C with a slight decomposition. It sublimes in a vacuum as low as 70&nbsp;°C. Being a molecular with four perchlorate ligands, it is an unusual example of a transition metal perchlorate complex.

Properties

In Ti(ClO<sub>4</sub>)<sub>4</sub>, the four perchlorate groups binds as bidentate ligands. Thus the Ti center is bound to eight oxygen atoms. So the molecule could also be called tetrakis(perchlorato-O,O)titanium(IV).

In the solid form it forms monoclinic crystals, with unit cell parameters a=12.451 b=7.814 c=12.826&nbsp;Å α=108.13. Unit cell volume is 1186&nbsp;Å<sup>3</sup> at -100&nbsp;°C. There are four molecules per unit cell.

It reacts with petrolatum, nitromethane, acetonitrile, dimethylformamide, and over 25&nbsp;°C with carbon tetrachloride.

Titanyl perchlorate form solvates with water, dimethyl sulfoxide, dioxane, pyridine-N-oxide, and quinoline-N-oxide.

Thermolysis of titanium perchlorate gives TiO<sub>2</sub>, ClO<sub>2</sub> and dioxygen O<sub>2</sub> The titanyl species TiO(ClO<sub>4</sub>)<sub>2</sub> is an intermediate in this decomposition.

Ti(ClO<sub>4</sub>)<sub>4</sub> → TiO<sub>2</sub> + 4ClO<sub>2</sub> + 3O<sub>2</sub> ΔH = .

Formation

Titanium perchlorate can be formed by reacting titanium tetrachloride with perchloric acid enriched in dichlorine heptoxide. Another way uses titanium tetrachloride with dichlorine hexoxide. This forms a complex with Cl<sub>2</sub>O<sub>6</sub> which when warmed to 55&nbsp;°C in a vacuum, sublimes and can crystallise the pure anhydrous product from the vapour.

Related

In the salt dicaesium hexaperchloratotitanate, Cs<sub>2</sub>Ti(ClO<sub>4</sub>)<sub>6</sub> the perchlorate groups are monodentate, connected by one oxygen to titanium.

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

A polymeric oxychlorperchlorato compound of titanium, Ti<sub>6</sub>O<sub>4</sub>Cl<sub>x</sub>(ClO<sub>4</sub>)<sub>16−x</sub>, is made from excess TiCl<sub>4</sub> and dichlorine hexoxide. This has a varying composition, and ranges from light to dark yellow.

References