Oxycation
Template:Short description
An oxycation, or oxocation, is an ion with the generic formula A
xOz+
y (where A represents a chemical element and O represents an oxygen atom). Their names normally end with the suffix "-ium" or "-yl".[1]
Isolable oxycations
A few salts of oxycations have been reported. They are all associated with lighter main group elements. The nitrogen-containing cations are Page Module:Chem2/styles.css has no content.NO+ and NO+
2. The latter is the active species in nitration reactions.
The Friedel-Crafts reaction is a classical organic reaction for attachment of acyl groups to arenes. The active acylating agent is often an acylium ion, several of which have been isolated..[2][3]
Oxycation nomenclature
Main group species
- Page Module:Chem2/styles.css has no content.NO+ - example: nitrosyl tetrafluoroborate
- NO+
2 - example: nitronium tetrafluoroborate - ClO+
2 - example: chloryl hexafluororuthenate[4]
More complicated oxycations include species like SOF3+.[5] Aluminyl, antimonyl, bismuthyl derivatives more closely resemble the situation for transition metal oxy cations in the sense that they are bonded to many Lewis bases. The cation [Bi6(O)4(OH)4]6+, a face-capped octahedral cluster, is one example.[6]
Transition metal species
Many transition compounds that contain an oxo ligand can be viewed as salts of a hypothetical "oxycation." In condensed phase, they are always complexed with strong Lewis bases.
- Page Module:Chem2/styles.css has no content.TiO2+ - example: titanyl sulfate, Page Module:Chem2/styles.css has no content.Ti(O)SO4(H2O).[7]
- Page Module:Chem2/styles.css has no content.VO3+ - example: vanadyl chloride, VOCl3
- Page Module:Chem2/styles.css has no content.VO2+ - example: vanadyl phosphate, VO(HPO4)
- CrO22+ - example: chromyl chloride, CrO2Cl2[8]
- MoO3+ - molybdenyl chloride, MoOCl3.[9]
- FeO2+ - examples include many ferryl intermediates
Actinide species
- Page Module:Chem2/styles.css has no content.PaO3+
- UO+
2,[10] NpO+
2,[11] PuO+
2, AmO+
2 - UO2+
2, NpO2+
2,[11] PuO2+
2, AmO2+
2
Oxycations in the gas-phase
While species like vanadyl (VO2+ and VO3+) do not exist in solution, some oxycations can be generated in the vacuum chamber of mass spectrometers. Using ion cyclotron resonance, these oxy cations have been shown to react even with simple hydrocarbons, attesting to the high reactivity.[12]
See also
References
Page Template:Reflist/styles.css has no content.
- ^ However, the International Union of Pure and Applied Chemistry standard book on nomenclature of inorganic chemistry does not mention "oxycation". Page Module:Citation/CS1/styles.css has no content.Union internationale de chimie pure et appliquée, ed. (2005). Nomenclature of inorganic chemistry: IUPAC recommendations 2005 (PDF). Cambridge: Royal society of chemistry. ISBN 978-0-85404-438-2. Retrieved 2025-05-22.
- ^ a b Page Module:Citation/CS1/styles.css has no content.Davlieva, Milya G.; Lindeman, Sergey V.; Neretin, Ivan S.; Kochi, Jay K. (2004). "Structural effects of carbon monoxide coordination to carbon centers. σ and π Bindings in aliphatic acyl versus aromatic aroyl cations". New Journal of Chemistry. 28 (12): 1568. doi:10.1039/B407654K.
- ^ Page Module:Citation/CS1/styles.css has no content.Boer, F. Peter (1968). "Crystal structure of a Friedel-Crafts intermediate. Methyloxocarbonium hexafluoroantimonate". Journal of the American Chemical Society. 90 (24): 6706–6710. doi:10.1021/ja01026a025.
- ^ Page Module:Citation/CS1/styles.css has no content.Bougon, R.; Cicha, W. V.; Lance, M.; Meublat, L.; Nierlich, M.; Vigner, J. (1991). "Preparation characterization and crystal structure of chloryl hexafluororuthenate(1-). Crystal structure of [ClF
2]+
[RuF
6]−
". Inorganic Chemistry. 30 (1): 102–109. doi:10.1021/ic00001a019. - ^ Page Module:Citation/CS1/styles.css has no content.Brownstein, M.; Dean, P. A. W.; Gillespie, R. J. (1970). "The Trifluorosulphur(VI) Oxide Cation, SOF3+". Journal of the Chemical Society D: Chemical Communications: 9. doi:10.1039/C29700000009.
- ^ Page Module:Citation/CS1/styles.css has no content.Sundvall, Bengt (1983). "Crystal Structure of Tetraoxotetrahydroxohexabismuth (III) Perchlorate Heptahydrate, Bi6O4(HO)4(ClO4)6.7H2O: An X-ray and Neutron Diffraction Study". Inorganic Chemistry. 22 (13): 1906–1912. doi:10.1021/ic00155a017.
- ^ Page Module:Citation/CS1/styles.css has no content.Gatehouse, B. M.; Platts, S. N.; Williams, T. B. (1993). "Structure of Anhydrous Titanyl Sulfate, Titanyl Sulfate Monohydrate and Prediction of a New Structure". Acta Crystallographica Section B. 49 (3): 428–435. Bibcode:1993AcCrB..49..428G. doi:10.1107/S010876819201320X.
- ^ Page Module:Citation/CS1/styles.css has no content.Sisler, Harry H. (1946). "Chromyl Chloride [Chromium(VI) Dioxychloride]". Inorganic Syntheses. Vol. 2. pp. 205–207. doi:10.1002/9780470132333.ch63. ISBN 9780470132333.
{{cite book}}: ISBN / Date incompatibility (help) - ^ Page Module:Citation/CS1/styles.css has no content.Olah, George; Welch, John; Surya Prakash, G.; Ho, Tse-Lok (2002). "Synthetic Methods and Reactions; XXIV1. Oxidative Cleavage of Hydrazones with Molybdenyl Chloride (MoOCl3) or Molybdenum Hexafluoride and Reductive Cleavage of Oximes with Molybdenyl Chloride/Zinc". Synthesis. 1976 (12): 808–809. doi:10.1055/s-1976-24211.
- ^ Page Module:Citation/CS1/styles.css has no content.Österreichische Chemiker-Zeitung (in Deutsch). Vol. 66. Springer. 1965. p. 52. Retrieved 21 May 2025.
- ^ a b Template:Cite Q
- ^ Page Module:Citation/CS1/styles.css has no content.Gunay, Ahmet; Theopold, Klaus H. (2010). "C−H Bond Activations by Metal Oxo Compounds". Chemical Reviews. 110 (2): 1060–1081. doi:10.1021/cr900269x. PMID 20143877.
