Dichlorine hexoxide

<h2 id="molecular-structure">Molecular structure</h2>
It was originally reported to exist as the monomeric chlorine trioxide ClO3 in gas phase,<a class="footnote-ref" id="fnref:2" href="#fn:2">2</a> but was later shown to remain an oxygen-bridged dimer after evaporation and until thermal decomposition into <a href="/facts/Chlorine_perchlorate/H18164qT">chlorine perchlorate</a>, Cl2O4, and oxygen.<a class="footnote-ref" id="fnref:3" href="#fn:3">3</a> The compound ClO3 was then rediscovered.<a class="footnote-ref" id="fnref:4" href="#fn:4">4</a>
It is a dark red fuming liquid at room temperature that crystallizes as a red ionic compound, chloryl perchlorate, [ClO2]+[ClO4]−. The red color shows the presence of <a href="/facts/Chloryl/gIaKL6IT">chloryl</a> 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).

<h2 id="properties">Properties</h2>
Cl2O6 is <a href="/facts/Diamagnetic/dgFavn9K">diamagnetic</a> and is a very strong oxidizing agent. Although stable at room temperature, it explodes violently on contact with organic compounds<a class="footnote-ref" id="fnref:5" href="#fn:5">5</a> It is a strong dehydrating agent:

Cl2O6 + H2O → <a href="/facts/HClO4/gjhK386J">HClO4</a> + <a href="/facts/HClO3/Cc7m9mg6">HClO3</a>
Many reactions involving Cl2O6 reflect its ionic structure, [ClO2]+[ClO4]−, including the following:<a class="footnote-ref" id="fnref:6" href="#fn:6">6</a>

<a href="/facts/NO2F/q7xYXaGm">NO2F</a> + Cl2O6 → <a href="/facts/Nitronium_perchlorate/0rbP8S2I">[NO2]+ClO−4</a> + <a href="/facts/ClO2F/r0Y1zczL">ClO2F</a>
<a href="/facts/Nitric_oxide/UvhdvDzp">NO</a> + Cl2O6 → <a href="/facts/Nitrosyl_perchlorate/JpYez1JI">[NO]+ClO−4</a> + <a href="/facts/Chlorine_dioxide/1K7ybEdW">ClO2</a>
2 <a href="/facts/V2O5/LPtvz4pq">V2O5</a> + 12 Cl2O6 → 4 VO(ClO4)3 + 12 ClO2 + 3 <a href="/facts/Oxygen/acyn6o8r">O2</a>
<a href="/facts/SnCl4/MgGG3FJJ">SnCl4</a> + 6 Cl2O6 → [ClO2]2[Sn(ClO4)6] + 4 ClO2 + 2 <a href="/facts/Chlorine/y27UwYBM">Cl2</a>
It reacts with <a href="/facts/Gold/1znknojp">gold</a> to produce the <a href="/facts/Chloryl/gIaKL6IT">chloryl</a> salt <a href="/facts/Chloryl_tetraperchloratoaurate/nJPnIHs0">[ClO2]+[Au(ClO4)4]−</a>:<a class="footnote-ref" id="fnref:7" href="#fn:7">7</a> 

2 Au + 6 Cl2O6 → 2 [ClO2]+[Au(ClO4)4]− + Cl2
Several other <a href="/facts/Transition_metal_perchlorate_complexes/LxdhUe9u">transition metal perchlorate complexes</a> are prepared using dichlorine hexoxide.
Nevertheless, it can also react as a source of the ClO3 radical:

2 <a href="/facts/AsF5/4478LA9F">AsF5</a> + Cl2O6 → 2 ClO3AsF5
<h2 id="synthesis">Synthesis</h2>
4 <a href="/facts/Chlorine_dioxide/1K7ybEdW">ClO2</a> + 2 <a href="/facts/Ozone/o0E5gn2p">O3</a> → 2 Cl2O6 + <a href="/facts/Oxygen/acyn6o8r">O2</a> (under <a href="/facts/Ultraviolet_light/kncBUqn5">ultraviolet light</a>)

<h2 id="references">References</h2>

<ol>
<li id="fn:1">Jean-Louis Pascal; Frédéric Favier (1998). "Inorganic perchlorato complexes". Coordination Chemistry Reviews. 178–180 (1): 865–902. doi:10.1016/S0010-8545(98)00102-7. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></li>
<li id="fn:2">C. F. Goodeve, F. A. Todd (1933). "Chlorine Hexoxide and Chlorine Trioxide". Nature. 132 (3335): 514–515. Bibcode:1933Natur.132..514G. doi:10.1038/132514b0. S2CID 4116929. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></li>
<li id="fn:3">Lopez, Maria; Juan E. Sicre (1990). "Physicochemical properties of chlorine oxides. 1. Composition, ultraviolet spectrum, and kinetics of the thermolysis of gaseous dichlorine hexoxide". J. Phys. Chem. 94 (9): 3860–3863. doi:10.1021/j100372a094. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></li>
<li id="fn:4">Grothe, Hinrich; Willner, Helge (1994). "Chlorine Trioxide: Spectroscopic Properties, Molecular Structure, and Photochemical Behavior". Angew. Chem. Int. Ed. 33 (14): 1482–1484. doi:10.1002/anie.199414821. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></li>
<li id="fn:5">Mary Eagleson (1994). Concise encyclopedia chemistry. Walter de Gruyter. p. 215. ISBN 3-11-011451-8. <a href="3-11-011451-8" target="_blank">3-11-011451-8</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></li>
<li id="fn:6">Harry Julius Emeléus, Alan George Sharpe (1963). Advances in Inorganic Chemistry and Radiochemistry. Academic Press. p. 65. ISBN 0-12-023605-2. {{cite book}}: ISBN / Date incompatibility (help) <a href="0-12-023605-2" target="_blank">0-12-023605-2</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></li>
<li id="fn:7">Cunin, Frédérique; Catherine Deudon; Frédéric Favier; Bernard Mula; Jean Louis Pascal (2002). "First anhydrous gold perchlorato complex: [ClO2]+[Au(ClO4)4]−. Synthesis and molecular and crystal structure analysis". Inorganic Chemistry. 41 (16): 4173–4178. doi:10.1021/ic020161z. PMID 12160405. {{cite journal}}: templatestyles stripmarker in |title= at position 43 (help) <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></li>
</ol>

Dichlorine hexoxide open-in-new

Dichlorine hexoxide