Chemistry:Xenon compounds

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Short description: Chemical compounds containing at least one xenon atom

Xenon compounds are compounds containing the element xenon (Xe). After Neil Bartlett's discovery in 1962 that xenon can form chemical compounds, a large number of xenon compounds have been discovered and described. Almost all known xenon compounds contain the electronegative atoms fluorine or oxygen. The chemistry of xenon in each oxidation state is analogous to that of the neighboring element iodine in the immediately lower oxidation state.[1]

Halides

A model of planar chemical molecule with a blue center atom (Xe) symmetrically bonded to four peripheral atoms (fluorine).
Xenon tetrafluoride
Many cubic transparent crystals in a petri dish.
XeF4 crystals, 1962

Three fluorides are known: XeF2, XeF4, and XeF6. XeF is theorized to be unstable.[2] These are the starting points for the synthesis of almost all xenon compounds.

The solid, crystalline difluoride XeF2 is formed when a mixture of fluorine and xenon gases is exposed to ultraviolet light.[3] The ultraviolet component of ordinary daylight is sufficient.[4] Long-term heating of XeF2 at high temperatures under an NiF2 catalyst yields XeF6.[5] Pyrolysis of XeF6 in the presence of NaF yields high-purity XeF4.[6]

The xenon fluorides behave as both fluoride acceptors and fluoride donors, forming salts that contain such cations as XeF+ and Xe2F+3, and anions such as XeF−5, XeF−7, and XeF2−8. The green, paramagnetic Xe+2 is formed by the reduction of XeF2 by xenon gas.[1]

XeF2 also forms coordination complexes with transition metal ions. More than 30 such complexes have been synthesized and characterized.[5]

Whereas the xenon fluorides are well characterized, the other halides are not. Xenon dichloride, formed by the high-frequency irradiation of a mixture of xenon, fluorine, and silicon or carbon tetrachloride,[7] is reported to be an endothermic, colorless, crystalline compound that decomposes into the elements at 80 °C. However, XeCl2 may be merely a van der Waals molecule of weakly bound Xe atoms and Cl2 molecules and not a real compound.[8] Theoretical calculations indicate that the linear molecule XeCl2 is less stable than the van der Waals complex.[9] Xenon tetrachloride and xenon dibromide are more unstable that they cannot be synthesized by chemical reactions. They were created by radioactive decay of 129ICl−4 and 129IBr−2, respectively.[10][11]

Oxides and oxohalides

Three oxides of xenon are known: xenon trioxide (XeO3) and xenon tetroxide (XeO4), both of which are dangerously explosive and powerful oxidizing agents, and xenon dioxide (XeO2), which was reported in 2011 with a coordination number of four.[12] XeO2 forms when xenon tetrafluoride is poured over ice. Its crystal structure may allow it to replace silicon in silicate minerals.[13] The XeOO+ cation has been identified by infrared spectroscopy in solid argon.[14]

Xenon does not react with oxygen directly; the trioxide is formed by the hydrolysis of XeF6:[15]

XeF6 + 3 H2O → XeO3 + 6 HF

XeO3 is weakly acidic, dissolving in alkali to form unstable xenate salts containing the HXeO−4 anion. These unstable salts easily disproportionate into xenon gas and perxenate salts, containing the XeO4−6 anion.[16]

Barium perxenate, when treated with concentrated sulfuric acid, yields gaseous xenon tetroxide:[7]

Ba2XeO6 + 2 H2SO4 → 2 BaSO4 + 2 H2O + XeO4

To prevent decomposition, the xenon tetroxide thus formed is quickly cooled into a pale-yellow solid. It explodes above −35.9 °C into xenon and oxygen gas, but is otherwise stable.

A number of xenon oxyfluorides are known, including XeOF2, XeOF4, XeO2F2, and XeO3F2. XeOF2 is formed by reacting OF2 with xenon gas at low temperatures. It may also be obtained by partial hydrolysis of XeF4. It disproportionates at −20 °C into XeF2 and XeO2F2.[17] XeOF4 is formed by the partial hydrolysis of XeF6...[18]

XeF6 + H2O → XeOF4 + 2 HF

...or the reaction of XeF6 with sodium perxenate, Na4XeO6. The latter reaction also produces a small amount of XeO3F2.

XeO2F2 is also formed by partial hydrolysis of XeF6.[19]

XeF6 + 2 H2O → XeO2F2 + 4 HF

XeOF4 reacts with CsF to form the XeOF−5 anion,[17][20] while XeOF3 reacts with the alkali metal fluorides KF, RbF and CsF to form the XeOF−4 anion.[21]

Other compounds

Xenon can be directly bonded to a less electronegative element than fluorine or oxygen, particularly carbon.[22] Electron-withdrawing groups, such as groups with fluorine substitution, are necessary to stabilize these compounds.[16] Numerous such compounds have been characterized, including:[17][23]

  • C6F5–Xe+–N≡C–CH3, where C6F5 is the pentafluorophenyl group.
  • [C6F5]2Xe
  • C6F5–Xe–C≡N
  • C6F5–Xe–F
  • C6F5–Xe–Cl
  • C2F5–C≡C–Xe+
  • [CH3]3C–C≡C–Xe+
  • C6F5–XeF+2
  • (C6F5Xe)2Cl+

Other compounds containing xenon bonded to a less electronegative element include F–Xe–N(SO2F)2 and F–Xe–BF2. The latter is synthesized from dioxygenyl tetrafluoroborate, O2BF4, at −100 °C.[17][24]

An unusual ion containing xenon is the tetraxenonogold(II) cation, AuXe2+4, which contains Xe–Au bonds.[25] This ion occurs in the compound AuXe4(Sb2F11)2, and is remarkable in having direct chemical bonds between two notoriously unreactive atoms, xenon and gold, with xenon acting as a transition metal ligand. A similar mercury complex (HgXe)(Sb3F17) (formulated as [HgXe2+][Sb2F11–][SbF6–]) is also known.[26]

The compound Xe2Sb2F11 contains a Xe–Xe bond, the longest element-element bond known (308.71 pm = 3.0871 Å).[27]

In 1995, M. Räsänen and co-workers, scientists at the University of Helsinki in Finland , announced the preparation of xenon dihydride (HXeH), and later xenon hydride-hydroxide (HXeOH), hydroxenoacetylene (HXeCCH), and other Xe-containing molecules.[28] In 2008, Khriachtchev et al. reported the preparation of HXeOXeH by the photolysis of water within a cryogenic xenon matrix.[29] Deuterated molecules, HXeOD and DXeOH, have also been produced.[30]

Clathrates and excimers

In addition to compounds where xenon forms a chemical bond, xenon can form clathrates—substances where xenon atoms or pairs are trapped by the crystalline lattice of another compound. One example is xenon hydrate (Xe·​5 3⁄4H2O), where xenon atoms occupy vacancies in a lattice of water molecules.[31] This clathrate has a melting point of 24 °C.[32] The deuterated version of this hydrate has also been produced.[33] Another example is xenon hydride (Xe(H2)8), in which xenon pairs (dimers) are trapped inside solid hydrogen.[34] Such clathrate hydrates can occur naturally under conditions of high pressure, such as in Lake Vostok underneath the Antarctic ice sheet.[35] Clathrate formation can be used to fractionally distill xenon, argon and krypton.[36]

Xenon can also form endohedral fullerene compounds, where a xenon atom is trapped inside a fullerene molecule. The xenon atom trapped in the fullerene can be observed by 129Xe nuclear magnetic resonance (NMR) spectroscopy. Through the sensitive chemical shift of the xenon atom to its environment, chemical reactions on the fullerene molecule can be analyzed. These observations are not without caveat, however, because the xenon atom has an electronic influence on the reactivity of the fullerene.[37]

When xenon atoms are in the ground energy state, they repel each other and will not form a bond. When xenon atoms becomes energized, however, they can form an excimer (excited dimer) until the electrons return to the ground state. This entity is formed because the xenon atom tends to complete the outermost electronic shell by adding an electron from a neighboring xenon atom. The typical lifetime of a xenon excimer is 1–5 nanoseconds, and the decay releases photons with wavelengths of about 150 and 173 nm.[38][39] Xenon can also form excimers with other elements, such as the halogens bromine, chlorine, and fluorine.[40]

References

  1. ↑ 1.0 1.1 Harding, Charlie; Johnson, David Arthur; Janes, Rob (2002). Elements of the p block. Great Britain: Royal Society of Chemistry. pp. 93–94. ISBN 0-85404-690-9. https://books.google.com/books?id=W0HW8wgmQQsC&pg=PA93. 
  2. ↑ Dean H Liskow; Henry F Schaefer III; Paul S Bagus; Bowen Liu (1973). "Probable nonexistence of xenon monofluoride as a chemically bound species in the gas phase". J Am Chem Soc 95 (12): 4056–57. doi:10.1021/ja00793a042. 
  3. ↑ Weeks, James L.; Chernick, Cedric; Matheson, Max S. (1962). "Photochemical Preparation of Xenon Difluoride". Journal of the American Chemical Society 84 (23): 4612–13. doi:10.1021/ja00882a063. 
  4. ↑ Streng, L. V.; Streng, A. G. (1965). "Formation of Xenon Difluoride from Xenon and Oxygen Difluoride or Fluorine in Pyrex Glass at Room Temperature". Inorganic Chemistry 4 (9): 1370–71. doi:10.1021/ic50031a035. 
  5. ↑ 5.0 5.1 Tramšek, Melita; Žemva, Boris (December 5, 2006). "Synthesis, Properties and Chemistry of Xenon(II) Fluoride". Acta Chimica Slovenica 53 (2): 105–16. doi:10.1002/chin.200721209. 
  6. ↑ Ogrin, Tomaz; Bohinc, Matej; Silvnik, Joze (1973). "Melting-point determinations of xenon difluoride-xenon tetrafluoride mixtures". Journal of Chemical and Engineering Data 18 (4): 402. doi:10.1021/je60059a014. 
  7. ↑ 7.0 7.1 Scott, Thomas; Eagleson, Mary (1994). "Xenon Compounds". Concise encyclopedia chemistry. Walter de Gruyter. p. 1183. ISBN 3-11-011451-8. https://books.google.com/books?id=Owuv-c9L_IMC&pg=PA1183. 
  8. ↑ Proserpio, Davide M.; Hoffmann, Roald; Janda, Kenneth C. (1991). "The xenon-chlorine conundrum: van der Waals complex or linear molecule?". Journal of the American Chemical Society 113 (19): 7184–89. doi:10.1021/ja00019a014. 
  9. ↑ Richardson, Nancy A.; Hall, Michael B. (1993). "The potential energy surface of xenon dichloride". The Journal of Physical Chemistry 97 (42): 10952–54. doi:10.1021/j100144a009. 
  10. ↑ Bell, C.F. (2013). Syntheses and Physical Studies of Inorganic Compounds. Elsevier Science. p. 143. ISBN 978-1-48328060-8. 
  11. ↑ Cockett, A.H.; Smith, K.C.; Bartlett, N. (2013). The Chemistry of the Monatomic Gases: Pergamon Texts in Inorganic Chemistry. Elsevier Science. p. 292. ISBN 978-1-48315736-8. 
  12. ↑ Brock, D.S.; Schrobilgen, G.J. (2011). "Synthesis of the missing oxide of xenon, XeO2, and its implications for Earth's missing xenon". Journal of the American Chemical Society 133 (16): 6265–9. doi:10.1021/ja110618g. PMID 21341650. 
  13. ↑ "Chemistry: Where did the xenon go?". Nature 471 (7337): 138. 2011. doi:10.1038/471138d. Bibcode: 2011Natur.471T.138.. 
  14. ↑ Zhou, M.; Zhao, Y.; Gong, Y.; Li, J. (2006). "Formation and Characterization of the XeOO+ Cation in Solid Argon". Journal of the American Chemical Society 128 (8): 2504–5. doi:10.1021/ja055650n. PMID 16492012. 
  15. ↑ Holloway, John H.; Hope, Eric G. (1998). A. G. Sykes. ed. Advances in Inorganic Chemistry Press. Academic. p. 65. ISBN 0-12-023646-X. https://books.google.com/books?id=6iqXRtz6p3QC&pg=PA65. 
  16. ↑ 16.0 16.1 Henderson, W. (2000). Main group chemistry. Great Britain: Royal Society of Chemistry. pp. 152–53. ISBN 0-85404-617-8. https://books.google.com/books?id=twdXz1jfVOsC&pg=PA152. 
  17. ↑ 17.0 17.1 17.2 17.3 Mackay, Kenneth Malcolm; Mackay, Rosemary Ann; Henderson, W. (2002). Introduction to modern inorganic chemistry (6th ed.). CRC Press. pp. 497–501. ISBN 0-7487-6420-8. https://books.google.com/books?id=LpJPWKT3PNcC&pg=PA497. 
  18. ↑ Smith, D. F. (1963). "Xenon Oxyfluoride". Science 140 (3569): 899–900. doi:10.1126/science.140.3569.899. PMID 17810680. Bibcode: 1963Sci...140..899S. 
  19. ↑ "P Block Elements" (in English). Chemistry Textbook Part - 1 for Class XII (October 2022 ed.). NCERT. 2007. p. 204. ISBN 9788174506481. https://ncert.nic.in/ncerts/l/lech107.pdf. 
  20. ↑ Christe, K. O.; Dixon, D. A.; Sanders, J. C. P.; Schrobilgen, G. J.; Tsai, S. S.; Wilson, W. W. (1995). "On the Structure of the [XeOF5]− Anion and of Heptacoordinated Complex Fluorides Containing One or Two Highly Repulsive Ligands or Sterically Active Free Valence Electron Pairs". Inorg. Chem. 34 (7): 1868–1874. doi:10.1021/ic00111a039. 
  21. ↑ Christe, K. O.; Schack, C. J.; Pilipovich, D. (1972). "Chlorine trifluoride oxide. V. Complex formation with Lewis acids and bases". Inorg. Chem. 11 (9): 2205–2208. doi:10.1021/ic50115a044. 
  22. ↑ Holloway, John H.; Hope, Eric G. (1998). Advances in Inorganic Chemistry. Contributor A. G. Sykes. Academic Press. pp. 61–90. ISBN 0-12-023646-X. https://books.google.com/books?id=6iqXRtz6p3QC&pg=PA61. 
  23. ↑ Frohn, H.; Theißen, Michael (2004). "C6F5XeF, a versatile starting material in xenon–carbon chemistry". Journal of Fluorine Chemistry 125 (6): 981–988. doi:10.1016/j.jfluchem.2004.01.019. 
  24. ↑ Goetschel, Charles T.; Loos, Karl 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. 
  25. ↑ Li, Wai-Kee; Zhou, Gong-Du; Mak, Thomas C. W. (2008). Gong-Du Zhou. ed. Advanced Structural Inorganic Chemistry. Oxford University Press. p. 678. ISBN 978-0-19-921694-9. https://books.google.com/books?id=2qAa5hp6KX4C&pg=PA678. 
  26. ↑ Hwang, In-Chul; Seidel, Stefan; Seppelt, Konrad (2003-09-22). "Gold( I ) and Mercury( II ) Xenon Complexes" (in en). Angewandte Chemie International Edition 42 (36): 4392–4395. doi:10.1002/anie.200351208. ISSN 1433-7851. PMID 14502720. https://onlinelibrary.wiley.com/doi/10.1002/anie.200351208. 
  27. ↑ Li, Wai-Kee; Zhou, Gong-Du; Mak, Thomas C. W. (2008). Advanced Structural Inorganic Chemistry. Oxford University Press. p. 674. ISBN 978-0-19-921694-9. https://archive.org/details/advancedstructur00liwa. 
  28. ↑ Gerber, R. B. (2004). "Formation of novel rare-gas molecules in low-temperature matrices". Annual Review of Physical Chemistry 55 (1): 55–78. doi:10.1146/annurev.physchem.55.091602.094420. PMID 15117247. Bibcode: 2004ARPC...55...55G. 
  29. ↑ Khriachtchev, Leonid; Isokoski, Karoliina; Cohen, Arik; Räsänen, Markku; Gerber, R. Benny (2008). "A Small Neutral Molecule with Two Noble-Gas Atoms: HXeOXeH". Journal of the American Chemical Society 130 (19): 6114–8. doi:10.1021/ja077835v. PMID 18407641. 
  30. ↑ Pettersson, Mika; Khriachtchev, Leonid; Lundell, Jan; Räsänen, Markku (1999). "A Chemical Compound Formed from Water and Xenon: HXeOH". Journal of the American Chemical Society 121 (50): 11904–905. doi:10.1021/ja9932784. 
  31. ↑ Pauling, L. (1961). A molecular theory of general anesthesia. pp. 15–21. doi:10.1126/science.134.3471.15. PMID 13733483. Bibcode: 1961Sci...134...15P.  Reprinted as Pauling, Linus, ed (2001). Linus Pauling: Selected Scientific Papers. 2. River Edge, NJ: World Scientific. pp. 1328–34. ISBN 981-02-2940-2. https://books.google.com/books?id=2QduA19d_X8C&pg=PA1329. 
  32. ↑ Henderson, W. (2000). Main group chemistry. Great Britain: Royal Society of Chemistry. p. 148. ISBN 0-85404-617-8. https://books.google.com/books?id=twdXz1jfVOsC&pg=PA148. 
  33. ↑ Ikeda, Tomoko; Mae, Shinji; Yamamuro, Osamu; Matsuo, Takasuke; Ikeda, Susumu; Ibberson, Richard M. (November 23, 2000). "Distortion of Host Lattice in Clathrate Hydrate as a Function of Guest Molecule and Temperature". Journal of Physical Chemistry A 104 (46): 10623–30. doi:10.1021/jp001313j. Bibcode: 2000JPCA..10410623I. 
  34. ↑ Kleppe, Annette K.; Amboage, Mónica; Jephcoat, Andrew P. (2014). "New high-pressure van der Waals compound Kr(H2)4 discovered in the krypton-hydrogen binary system". Scientific Reports 4: 4989. doi:10.1038/srep04989. Bibcode: 2014NatSR...4E4989K. 
  35. ↑ McKay, C. P.; Hand, K. P.; Doran, P. T.; Andersen, D. T.; Priscu, J. C. (2003). "Clathrate formation and the fate of noble and biologically useful gases in Lake Vostok, Antarctica". Geophysical Research Letters 30 (13): 35. doi:10.1029/2003GL017490. Bibcode: 2003GeoRL..30.1702M. 
  36. ↑ Barrer, R. M.; Stuart, W. I. (1957). "Non-Stoichiometric Clathrate of Water". Proceedings of the Royal Society of London 243 (1233): 172–89. doi:10.1098/rspa.1957.0213. Bibcode: 1957RSPSA.243..172B. 
  37. ↑ Frunzi, Michael; Cross, R. James; Saunders, Martin (2007). "Effect of Xenon on Fullerene Reactions". Journal of the American Chemical Society 129 (43): 13343–6. doi:10.1021/ja075568n. PMID 17924634. https://figshare.com/articles/journal_contribution/2977702. 
  38. ↑ Silfvast, William Thomas (2004). Laser Fundamentals. Cambridge University Press. ISBN 0-521-83345-0. https://books.google.com/books?id=x3VB2iwSaxsC&pg=RA1-PA152. 
  39. ↑ Webster, John G. (1998). The Measurement, Instrumentation, and Sensors Handbook. Springer. ISBN 3-540-64830-5. https://books.google.com/books?id=b7UuZzf9ivIC&pg=PT2427. 
  40. ↑ McGhee, Charles; Taylor, Hugh R.; Gartry, David S.; Trokel, Stephen L. (1997). Excimer Lasers in Ophthalmology. Informa Health Care. ISBN 1-85317-253-7. https://books.google.com/books?id=pg0bUc_GcVoC&pg=PA4. 



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