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Trirhenium nonachloride
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<h2 id="structure-and-physical-properties">Structure and physical properties</h2> <p>As shown by <a href="/facts/X-ray_crystallography/WtI0F5DN">X-ray crystallography</a> trirhenium nonachloride consists of Re3Cl12 subunits that share three chloride <a href="/facts/Bridging_ligand/E4ytba8I">bridges</a> with adjacent clusters. The interconnected network of clusters forms sheets. Around each Re center are seven ligands, four bridging chlorides, one terminal chloride, and two Re-Re bonds.<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p> <p>The <a href="/facts/Water_of_crystallization/sbaKJNJX">hydrate</a> is molecular with the formula Re3Cl9(H2O)3.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> </p><p>The <a href="/facts/Standard_enthalpy_change_of_reaction/u5pffxVM">heat of oxidation</a> is evaluated according to the equation: </p> 1/3 Re3Cl9 + 4 OH− + 2 OCl− → ReO4− + 2 H2O + 5Cl− <p>The enthalpy for this process is 190.7 ± 0.2 kcal/mol.<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> </p> <h2 id="preparation-and-reactions">Preparation and reactions</h2> <p>The compound was discovered in 1932.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> Trirhenium nonachloride is efficiently prepared by thermal decomposition of <a href="/facts/Rhenium_pentachloride/K989aTxt">rhenium pentachloride</a> or hexachlororhenic(IV) acid:<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> </p> 3 ReCl5 → Re3Cl9 + 3 Cl2 <p>If the sample is vacuum <a href="/facts/Sublimation_(chemistry)/KDoKokMn">sublimed</a> at 500 °C, the resulting material is comparatively unreactive. The partially hydrated material such as Re3Cl9(H2O)4<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> can be more useful synthetically. Other synthetic methods include treating <a href="/facts/Rhenium/TzyqJYEn">rhenium</a> with <a href="/facts/Sulfuryl_chloride/UtEHXDb8">sulfuryl chloride</a>. This process is sometimes conducted with the addition of <a href="/facts/Aluminium_chloride/xrhvSxDr">aluminium chloride</a>.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> It is also obtained by heating Re2(O2CCH3)4Cl2 under HCl: </p> 3/2 Re2(O2CCH3)4Cl2 + 6 HCl → Re3Cl9 + 6 HO2CCH3 <p>Reaction of the tri- and pentachlorides gives <a href="/facts/Rhenium_tetrachloride/7fjwNJ7K">rhenium tetrachloride</a>: </p> 3 ReCl5 + Re3Cl9 → 6 ReCl4 <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Cotton, F. A.; Walton, R. A. "Multiple Bonds Between Metal Atoms" Oxford (Oxford): 1993. ISBN 0-19-855649-7. <a href="/wiki/ISBN_(identifier)" target="_blank">/wiki/ISBN_(identifier)</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Colton, R. Chemistry of rhenium and technetium. 965. <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Irmler, Manfred; Meyer, Gerd (1987). "Rhenium trichloride, ReCl3, and its 5/3-hydrate synthesis, crystal structure, and thermal expansion". Zeitschrift für Anorganische und Allgemeine Chemie. 552 (9): 81–89. doi:10.1002/zaac.19875520908. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Colton, R. Chemistry of rhenium and technetium. 965. <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Geilnann, W.; Wriuce, F. W.; Biltz. W.: Nachr. Ges. Wiss. Gottingen 1932, 579. <a href="/wiki/Wilhelm_Biltz" target="_blank">/wiki/Wilhelm_Biltz</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Lincoln, R.; Wilkinson, G. (1980). "Trirhenium Nonachloride". Inorg. Synth. 20: 44. doi:10.1002/9780470132517.ch12. ISBN 978-0-470-13251-7. <a href="978-0-470-13251-7" target="_blank">978-0-470-13251-7</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Irmler, Manfred; Meyer, Gerd (1987). "Rhenium trichloride, ReCl3, and its 5/3-hydrate synthesis, crystal structure, and thermal expansion". Zeitschrift für Anorganische und Allgemeine Chemie. 552 (9): 81–89. doi:10.1002/zaac.19875520908. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Colton, R. Chemistry of rhenium and technetium. 965. <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> </ol>