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Dichlorine hexoxide

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Title: Dichlorine hexoxide  
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Subject: List of inorganic compounds, ClO3, Chlorine perchlorate
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Dichlorine hexoxide

Dichlorine hexoxide
CAS number 12442-63-6 YesY
Molecular formula Cl2O6
Molar mass 166.901 g/mol
Appearance red liquid
Density 1.65 g/cm3
Melting point

3.5 °C

Boiling point

200 °C

Solubility in water Reacts
Main hazards oxidizer
 YesY (verify) (what is: YesY/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Dichlorine hexoxide is the chemical compound with the molecular formula , 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 , which may be thought of as the mixed anhydride of chloric and perchloric acids.

It is produced by reaction between chlorine dioxide and excess ozone:

2 + 2 → 2 + 2 + 2

Molecular structure

It was originally reported to exist as the monomeric chlorine trioxide ClO3 in gas phase,[1] but was later shown to remain an oxygen-bridged dimer after evaporation and until thermal decomposition into chlorine perchlorate, Cl2O4, and oxygen.[2]

It is a dark red fuming liquid at room temperature that crystallizes as a red ionic compound, chloryl perchlorate, . The red color shows the presence of chloryl ions. Thus, chlorine's formal oxidation state in this compound remains a mixture of chlorine (V) and chlorine (VII) both in the gas phase and when condensed; however by breaking one oxygen-chlorine bond some electron density does shifts towards the chlorine (VII).


Cl2O6 is diamagnetic and is a very strong oxidizing agent. Although stable at room temperature, it explodes violently on contact with organic compounds[3] and reacts with gold to produce the chloryl salt .[4] Many other reactions involving Cl2O6 reflect its ionic structure, , including the following:[5]

NO2F + Cl2O6 → NO2ClO4 + ClO2F
NO + Cl2O6 → NOClO4 + ClO2
2 V2O5 + 12 Cl2O6 → 4 VO(ClO4)3 + 12 ClO2 + 3 O2
SnCl4 + 6 Cl2O6 → [ClO2]2[Sn(ClO4)6] + 4 ClO2 + 2 Cl2
2Au + 6Cl2O6 → 2 + Cl2

Nevertheless, it can also react as a source of the ClO3 radical:

2 AsF5 + Cl2O6 → 2 ClO3AsF5


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