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Dioxygenyl
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<h2 id="structure-and-molecular-properties">Structure and molecular properties</h2> <p>O+2 has a <a href="/facts/Bond_order/Tdb1zgTc">bond order</a> of 2.5, and a <a href="/facts/Bond_length/rHHIBH6q">bond length</a> of 112.3 pm in solid O2[AsF6].<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> It is <a href="/facts/Isoelectronic/SbzuaI05">isoelectronic</a> with <a href="/facts/Nitric_oxide/UvhdvDzp">nitric oxide</a> and is paramagnetic.<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> The <a href="/facts/Bond_energy/q4be3EeR">bond energy</a> is 625.1 kJ mol−1 and the stretching frequency is 1858 <a href="/facts/Wavenumber/cLaLAeW5">cm−1</a>,<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> both of which are high relative to most of the molecules. </p> <h2 id="synthesis">Synthesis</h2> <p><a href="/facts/Neil_Bartlett_(chemist)/l9jReu2S">Neil Bartlett</a> demonstrated that <a href="/facts/Dioxygenyl_hexafluoroplatinate/AUcQD8RL">dioxygenyl hexafluoroplatinate</a> (O2PtF6), containing the dioxygenyl cation, can be prepared at room temperature by direct reaction of oxygen gas (O2) with <a href="/facts/Platinum_hexafluoride/Nqqdd4Xc">platinum hexafluoride</a> (PtF6):<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> </p> O2 + PtF6 → [O2]+[PtF6]− <p>The compound can also be prepared from a mixture of fluorine and oxygen gases in the presence of a <a href="/facts/Platinum/qJC6lQf7">platinum</a> sponge at 450 °C, and from <a href="/facts/Oxygen_difluoride/7WF0HL33">oxygen difluoride</a> (OF2) above 400 °C:<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> 6 OF2 + 2 Pt → 2 [O2][PtF6] + O2 <p>At lower temperatures (around 350 °C), <a href="/facts/Platinum_tetrafluoride/2WDL4mqw">platinum tetrafluoride</a> is produced instead of dioxygenyl hexafluoroplatinate.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> Dioxygenyl hexafluoroplatinate played a pivotal role in the discovery of <a href="/facts/Noble_gas_compound/vkIWeVeF">noble gas compounds</a>. The observation that PtF6 is a powerful enough oxidising agent to oxidise O2 (which has a first <a href="/facts/Ionization_potential/lezUajfA">ionization potential</a> of 12.2 <a href="/facts/Electron_volt/YMT1fqX9">eV</a>) led Bartlett to reason that it should also be able to oxidise <a href="/facts/Xenon/9E3XR69R">xenon</a> (first ionization potential 12.13 eV). His subsequent investigation yielded the first compound of a <a href="/facts/Noble_gas/j0yHMEAE">noble gas</a>, <a href="/facts/Xenon_hexafluoroplatinate/RtRHxpjp">xenon hexafluoroplatinate</a>.<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> </p><p>O+2 is also found in similar compounds of the form O2MF6, where M is <a href="/facts/Arsenic/k1c4f44D">arsenic</a> (As), <a href="/facts/Antimony/YsA7lVgT">antimony</a> (Sb),<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> <a href="/facts/Gold/1znknojp">gold</a> (Au),<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> <a href="/facts/Niobium/3zNI8AKp">niobium</a> (Nb), <a href="/facts/Ruthenium/uzCm4ufn">ruthenium</a> (Ru), <a href="/facts/Rhenium/TzyqJYEn">rhenium</a> (Re), <a href="/facts/Rhodium/xmBd9aFG">rhodium</a> (Rh),<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> <a href="/facts/Vanadium/UvKkKTSm">vanadium</a> (V),<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> or <a href="/facts/Phosphorus/27xCeIqs">phosphorus</a> (P).<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> Other forms are also attested, including O2GeF5 and (O2)2SnF6.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> </p><p>The tetrafluoroborate and hexafluorophosphate salts may be prepared by the reaction of <a href="/facts/Dioxygen_difluoride/6lwT94AK">dioxygen difluoride</a> with <a href="/facts/Boron_trifluoride/2qa0NIH8">boron trifluoride</a> or <a href="/facts/Phosphorus_pentafluoride/VbqstNnq">phosphorus pentafluoride</a> at −126 °C:<a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a> </p> 2 O2F2 + 2 BF3 → 2 O2BF4 + F2 2 O2F2 + 2 PF5 → 2 O2PF6 + F2 <p>These compounds rapidly decompose at room temperature: </p> 2 O2BF4 → 2 O2 + F2 + 2 BF3 2 O2PF6 → 2 O2 + F2 + 2 PF5 <p>Some compounds including O2Sn2F9, O2Sn2F9·0.9HF, O2GeF5·HF, and O2[Hg(HF)]4(SbF6)9 can be made by ultraviolet irradiation of oxygen and fluorine dissolved in anhydrous hydrogen fluoride with a metal oxide.<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a> </p><p>All attempts to prepare O+2 with chloro anions like [O2]+[SbCl6]− met with failure. </p> <h2 id="reactions">Reactions</h2> <p>The reaction of O2BF4 with <a href="/facts/Xenon/9E3XR69R">xenon</a> at 173 K (−100 °C) produces a white solid believed to be F–Xe–BF2, containing an unusual xenon-boron bond:<a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> </p> 2 O2BF4 + 2 Xe → 2 O2 + F2 + 2 FXeBF2 <p>The dioxygenyl salts O2BF4 and O2AsF6 react with <a href="/facts/Carbon_monoxide/CKuLtEMJ">carbon monoxide</a> to give <a href="/facts/Oxalyl_fluoride/46ff480o">oxalyl fluoride</a>, C2O2F2, in high yield.<a class="footnote-ref" id="fnref:19" href="#fn:19"><sup>19</sup></a> </p> <h2 id="external-links">External links</h2> <ul><li> Media related to Dioxygenyl at Wikimedia Commons</li></ul> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Michael Clugston; Rosalind Flemming (2000). Advanced Chemistry, Oxford University Press, ISBN 0-19-914633-0, ISBN 978-0-19-914633-8, p. 355. <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>Foote, Christopher S.; Valentine, Joan S. (1995). Active oxygen in chemistry. Joel F. Liebman, A. Greenberg. Springer. ISBN 0-412-03441-7. <a href="0-412-03441-7" target="_blank">0-412-03441-7</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. p. 616 <a href="978-0-08-037941-8" target="_blank">978-0-08-037941-8</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5 <a href="0-471-19957-5" target="_blank">0-471-19957-5</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>J. Shamir; J. Binenboym; H. H. Claassen (1968). "The vibrational frequency of the O2+ cation". J. Am. Chem. Soc. 90 (22): 6223–6224. doi:10.1021/ja01024a054. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Bartlett, Neil; Lohmann, D. H. (1962). "Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O2]+[PtF6]−". J. Chem. Soc. 115: 5253–5261. doi:10.1039/jr9620005253. <a href="/wiki/Neil_Bartlett_(chemist)" target="_blank">/wiki/Neil_Bartlett_(chemist)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Bartlett, Neil; Lohmann, D. H. (1962). "Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O2]+[PtF6]−". J. Chem. Soc. 115: 5253–5261. doi:10.1039/jr9620005253. <a href="/wiki/Neil_Bartlett_(chemist)" target="_blank">/wiki/Neil_Bartlett_(chemist)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Bartlett, Neil; Lohmann, D. H. (1962). "Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O2]+[PtF6]−". J. Chem. Soc. 115: 5253–5261. doi:10.1039/jr9620005253. <a href="/wiki/Neil_Bartlett_(chemist)" target="_blank">/wiki/Neil_Bartlett_(chemist)</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Bartlett, Neil (1962). "Xenon hexafluoroplatinate(V), Xe+[PtF6]−". Proc. Chem. Soc.: 197–236. doi:10.1039/PS9620000197. <a href="/wiki/Neil_Bartlett_(chemist)" target="_blank">/wiki/Neil_Bartlett_(chemist)</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Young, A. R.; Hirata, T.; Morrow, S. I. (1964). "The Preparation of Dioxygenyl Salts from Dioxygen Difluoride". J. Am. Chem. Soc. 86 (1): 20–22. doi:10.1021/ja01055a006. <a href="/wiki/J._Am._Chem._Soc." target="_blank">/wiki/J._Am._Chem._Soc.</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>Nakajima, Tsuyoshi (1995). Fluorine-carbon and fluoride-carbon materials: chemistry, physics, and applications. CRC Press. ISBN 0-8247-9286-6. <a href="0-8247-9286-6" target="_blank">0-8247-9286-6</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> <li id="fn:12"><p>Vasile, Michael J.; Falconer, Warren E. (1975). "Vapour transport of dioxygenyl salts". J. Chem. Soc., Dalton Trans. 1975 (4): 316–318. doi:10.1039/DT9750000316. <a href="/wiki/J._Chem._Soc.,_Dalton_Trans." target="_blank">/wiki/J._Chem._Soc.,_Dalton_Trans.</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li> <li id="fn:13"><p>Holleman, Arnold F.; Wiberg, Egon (2001). Inorganic chemistry. Academic Press. p. 475. ISBN 0-12-352651-5. <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li> <li id="fn:14"><p>Solomon, Irvine J.; Brabets, Robert I.; Uenishi, Roy K.; Keith, James N.; McDonough, John M. (1964). "New Dioxygenyl Compounds". Inorg. Chem. 3 (3): 457. doi:10.1021/ic50013a036. <a href="/wiki/Inorg._Chem." target="_blank">/wiki/Inorg._Chem.</a> <a href="#fnref:14" class="footnote-back-ref">↩</a></p></li> <li id="fn:15"><p>Holleman, Arnold F.; Wiberg, Egon (2001). Inorganic chemistry. Academic Press. p. 475. ISBN 0-12-352651-5. <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:15" class="footnote-back-ref">↩</a></p></li> <li id="fn:16"><p>Solomon, Irvine J.; Brabets, Robert I.; Uenishi, Roy K.; Keith, James N.; McDonough, John M. (1964). "New Dioxygenyl Compounds". Inorg. Chem. 3 (3): 457. doi:10.1021/ic50013a036. <a href="/wiki/Inorg._Chem." target="_blank">/wiki/Inorg._Chem.</a> <a href="#fnref:16" class="footnote-back-ref">↩</a></p></li> <li id="fn:17"><p>Mazej, Zoran; Goreshnik, Evgeny (2020-02-03). "Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of α- and β-O2Sn2F9, O2Sn2F9·0.9HF, O2GeF5·HF, and O2[Hg(HF)]4(SbF6)9". Inorganic Chemistry. 59 (3): 2092–2103. doi:10.1021/acs.inorgchem.9b03518. ISSN 0020-1669. PMC 7307900. PMID 31942804. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7307900" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7307900</a> <a href="#fnref:17" class="footnote-back-ref">↩</a></p></li> <li id="fn:18"><p>Goetschel, C. T.; Loos, K. R. (1972). "Reaction of xenon with dioxygenyl tetrafluoroborate. Preparation of FXe-BF2". Journal of the American Chemical Society. 94 (9): 3018–3021. doi:10.1021/ja00764a022. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:18" class="footnote-back-ref">↩</a></p></li> <li id="fn:19"><p>Pernice, H.; Willner, H.; Eujen, R. (2001). "The reaction of dioxygenyl salts with 13CO Formation of F13C(O)13C(O)F". Journal of Fluorine Chemistry. 112 (2): 277–590. doi:10.1016/S0022-1139(01)00512-7. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:19" class="footnote-back-ref">↩</a></p></li> </ol>