:Titanium perchlorate
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| Watchedfields = changed
| verifiedrevid =
| Name = Titanium(IV) perchlorate
| ImageFile = Ti(ClO4)4.svg
| ImageSize = 150px
| ImageName = titanium perchlorate
| OtherNames =
|Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID =
| InChI = 1S/4ClHO4.Ti/c4*2-1(3,4)5;/h4*(H,2,3,4,5);/q;;;;+4/p-4
| InChIKey = SOCDLWOJPVKBHF-UHFFFAOYSA-J
| SMILES = [Ti](O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)O[Cl](=O)(=O)=O
| StdInChI_Ref =
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| CASNo = 60580-20-3
| CASNo2= 13498-15-2
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| UNII =
| PubChem = 14795113
}}
|Section2={{Chembox Properties
| Formula = Ti(ClO4)4
| Appearance = white crystals,
deliquescent
| Odor =
| Ti=1 | Cl=4 | O=16
| Density = 2.49 g/cm3 (anhydrous)
| Solubility = high
| Solubility1 =
| Solvent1 = carbon tetrachloride
| MeltingPtC = 85
| MeltingPt_notes = (anhydrous) slight decomposition
| BoilingPt = decomposition
}}
|Section7={{Chembox Hazards
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|Section8={{Chembox Related
| OtherCations = Zirconium perchlorate
Hafnium perchlorate
| OtherAnions = Titanium nitrate
}}
}}
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.
Properties
In Ti(ClO4)4, 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)'.{{cite book|last1=Macintyre|first1=Jane E.|title=Dictionary of Inorganic Compounds|date=1992|publisher=CRC Press|isbn=9780412301209|page=2963|url=https://books.google.com/books?id=9eJvoNCSCRMC&pg=PA2963|language=en}}
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.{{cite journal|last1=Fourati|first1=Mohieddine|last2=Chaabouni|first2=Moncef|last3=Belin|first3=Claude Henri|last4=Charbonnel|first4=Monique|last5=Pascal|first5=Jean Louis|last6=Potier|first6=Jacqueline|title=A strongly chelating bidentate perchlorate. New synthesis route and crystal structure determination of titanium(4+) perchlorate|journal=Inorganic Chemistry|date=April 1986|volume=25|issue=9|pages=1386–1390|doi=10.1021/ic00229a019}}
It reacts with petrolatum, nitromethane, acetonitrile, dimethylformamide, and over 25° with carbon tetrachloride.
Titanyl perchlorate form solvates with water, dimethyl sulfoxide, dioxane, pyridine-N-oxide, and quinoline-N-oxide.
Thermolysis of titanium perchlorate gives TiO2, ClO2 and dioxygen O2 The titanyl species TiO(ClO4)2 is an intermediate in this decomposition.{{cite journal|last1=Babaeva|first1=V. P.|last2=Rosolovskii|first2=V.|year=1974|title=Volatile titanium perchlorate|journal=Bulletin of the Academy of Sciences of the USSR Division of Chemical Science|volume=23|issue=11|pages=2330–2334|issn=0568-5230|doi=10.1007/BF00922105}}
:Ti(ClO4)4 → TiO2 + 4ClO2 + 3O2 ΔH = {{convert|+6|kcal/mol|abbr=on}}.
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 Cl2O6 which when warmed to 55° in a vacuum, sublimes and can crystallise the pure anhydrous product from the vapour.
Related
In the salt dicaesium hexaperchloratotitanate, Cs2Ti(ClO4)6 the perchlorate groups are monodentate, connected by one oxygen to titanium.{{cite journal|last1=Babaeva|first1=V. P.|last2=Rosolovskii|first2=V. Ya.|title=Production of cesium hexaperchloratotitanate by the reaction of titanium perchlorate with cesium perchlorate|journal=Bulletin of the Academy of Sciences of the USSR Division of Chemical Science|date=November 1975|volume=24|issue=11|pages=2278–2281|doi=10.1007/BF00921631}}
Titanium perchlorate can also form complexes with other ligands bound to the titanium atom including binol,{{cite journal|last1=Mikami|first1=Koichi|last2=Sawa|first2=Eiji|last3=Terada|first3=Masahiro|title=Asymmetric catalysis by chiral titanium perchlorate for carbonyl-ene cyclization|journal=Tetrahedron: Asymmetry|date=January 1991|volume=2|issue=12|pages=1403–1412|doi=10.1016/S0957-4166(00)80036-1}} and gluconic acid.{{cite book|last1=Guthrie|first1=R. D.|title=Carbohydrate Chemistry|date=1970|publisher=Royal Society of Chemistry|location=London|isbn=9780851860220|volume=3|page=144|url=https://books.google.com/books?id=d1SUAE2qD80C&pg=PA144|language=en}}
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.{{cite journal|last1=Fourati|first1=M.|last2=Chaabouni|first2=M.|last3=Pascal|first3=J.L.|last4=Potter|first4=J.|title=Synthesis and vibrational analysis of new anhydrous oxochloroperchlorato complexes of titanium IV|journal=Journal of Molecular Structure|date=March 1986|volume=143|issue=1–2|pages=147–150|doi=10.1016/0022-2860(86)85225-5|bibcode=1986JMoSt.143..147F}}
References
{{Reflist}}
{{Titanium compounds}}
{{perchlorates}}