Titanium perchlorate
Chemical compound From Wikipedia, the free encyclopedia
Titanium perchlorate, or more precisely titanium(IV) 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 sublimes in a vacuum as low as 70 °C. Being a molecular with four perchlorate ligands, it is an unusual example of a transition metal perchlorate complex.
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3D model (JSmol) |
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PubChem CID |
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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 |
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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).
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Properties
In Ti(ClO4)4, the four perchlorate groups binds as bidentate ligands. Thus the Ti center is bound to eight oxygen atoms.[2] So the molecule could also be called tetrakis(perchlorato-O,O')titanium(IV).[3]
In the solid form it forms 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 form solvates with water, dimethyl sulfoxide, dioxane, pyridine-N-oxide, and quinoline-N-oxide.[2]
Thermolysis of titanium perchlorate gives TiO2, ClO2 and dioxygen O2 The titanyl species TiO(ClO4)2 is an intermediate in this decomposition.[2]
- Ti(ClO4)4 → TiO2 + 4ClO2 + 3O2 ΔH = +6 kcal/mol (25 kJ/mol).[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
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