Fluoronium: Difference between revisions
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{{Short description|Ion}} |
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| ImageFile1 = Fluoronium-dimensions-2D.png |
| ImageFile1 = Fluoronium-dimensions-2D.png |
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| ImageFile1_Ref = {{chemboximage|correct|??}} |
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| ImageSize1 = 180 |
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| ImageName1 = Skeletal formula of fluoronium with assorted dimensions{{Citation|last1 = Diercksen|first1 = G. H. F.|last2 = von Niessen|first2 = W.|last3 = Kraemer|first3 = W. P.|title = SCF LCGO MO studies on the fluoronium ion {{chem|FH|2|+}} and its hydrogen bonding interaction with hydrogen fluoride FH|journal= Theoretical Chemistry Accounts: Theory, Computation, and Modeling|volume = 31|issue = 3|pages = 205–214|date = September 1973|doi = 10.1007/BF00526510|s2cid = 98637994}} |
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| ImageFileL1 = Fluoronium-3D-balls.png |
| ImageFileL1 = Fluoronium-3D-balls.png |
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| ImageFileL1_Ref = {{chemboximage|correct|??}} |
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| ImageSizeL1 = 131 |
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| ImageNameL1 = Ball-and-stick model of fluoronium |
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| ImageFileR1 = Fluoronium-3D-vdW.png |
| ImageFileR1 = Fluoronium-3D-vdW.png |
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| ImageFileR1_Ref = {{chemboximage|correct|??}} |
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| ImageSizeR1 = 131 |
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| ImageNameR1 = Spacefill model of fluoronium |
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| IUPACName = Fluoronium |
| IUPACName = Fluoronium |
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| SystematicName = Fluoranium |
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| SystematicName = Fluoranium<ref>{{Cite web|title = Fluoronium (CHEBI:50314)|url = https://www.ebi.ac.uk/chebi/searchId.do?chebiId=50314|work = Chemical Entities of Biological Interest (ChEBI)|location = UK|publisher = European Bioinformatics Institute}}</ref> |
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|Section1={{Chembox Identifiers |
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| CASNo = 12206-67-6 |
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| ChEBI = 50314 |
| ChEBI = 50314 |
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| SMILES = [FH2+] |
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| StdInChI = 1S/FH2/h1H2/q+1 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| InChI = 1/FH2/h1H2/q+1 |
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| StdInChIKey = YNESUKSMQODWNS-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| InChIKey = YNESUKSMQODWNS-UHFFFAOYAK |
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|Section2={{Chembox Properties |
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| Formula = H<sub>2</sub>F<sup>+</sup> |
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| ConjugateBase = [[Hydrogen fluoride]] |
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| MolarMass = 21.01428 g mol<sup>-1</sup> |
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| MolarMass = 21.01374 g mol<sup>−1</sup> |
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The '''fluoronium''' ion is an [[inorganic chemistry|inorganic]] [[ion#Anions and cations|cation]] with the [[chemical formula]] {{Chem|H|2|F|+}}. It is one of the cations found in [[fluoroantimonic acid]].<ref>{{Cite journal|last1=Esteves|first1=Pierre M.|last2=Ramírez-Solís|first2=Alejandro|last3=Mota|first3=Claudio J. A.|date=March 2002|title=The Nature of Superacid Electrophilic Species in HF/SbF5: A Density Functional Theory Study|journal=Journal of the American Chemical Society|volume=124|issue=11|pages=2672–2677|doi=10.1021/ja011151k|issn=0002-7863|pmid=11890818}}</ref> The structure of the salt with the {{Chem|Sb|2|F|11|-}} anion, has been determined.<ref>{{cite journal|last1=Mootz|first1=Dietrich|last2=Bartmann|first2=Klemens|date=1988|title=The Fluoronium Ions H<sub>2</sub>F<sup>+</sup> and {{chem|H|3|F|2|+}}: Characterization by Crystal Structure Analysis|url=|journal=Angewandte Chemie|volume=27|issue=3|pages=391–392|doi=10.1002/anie.198803911}}</ref><ref>{{Cite journal|last1 = Diercksen|first1 = G. H. F.|last2 = von Niessen|first2 = W.|last3 = Kraemer|first3 = W. P.|title = SCF LCGO MO studies on the fluoronium ion {{chem|FH|2|+}} and its hydrogen bonding interaction with hydrogen fluoride FH|journal= Theoretical Chemistry Accounts: Theory, Computation, and Modeling|volume = 31|issue = 3|pages = 205–214|date = 1973|doi = 10.1007/BF00526510|s2cid = 98637994}}</ref> The fluoronium ion is [[isoelectronic]] with the [[Properties of water|water]] molecule and the [[Azanide|azanide ion]]. |
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The '''fluoronium''' [[cation]], H<sub>2</sub>F<sup>+</sup>, is a [[polyatomic ion]] formed by [[protonation]] or self-ionic dissociation of [[hydrogen fluoride]]: |
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The term can also refer to organyl substituted species of type H–{{overset|+|F}}–R, R–{{overset|+|F}}–R, or R<sub>2</sub>C=F<sup>+</sup>. In contrast to the heavier halogens, which have long been known to form open-chain [[halonium ion]]s (such as [Me<sub>2</sub>Cl]<sup>+</sup>[Al(OTeF<sub>5</sub>)<sub>4</sub>]<sup>–</sup>)<ref>{{Cite journal|last1=Hämmerling|first1=Sebastian|last2=Thiele|first2=Günther|last3=Steinhauer|first3=Simon|last4=Beckers|first4=Helmut|last5=Müller|first5=Carsten|last6=Riedel|first6=Sebastian|date=2019|title=A Very Strong Methylation Agent: [Me2Cl][Al(OTeF5)4]|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201904007|journal=Angewandte Chemie International Edition|language=en|volume=58|issue=29|pages=9807–9810|doi=10.1002/anie.201904007|pmid=31050103 |s2cid=143434865 |issn=1521-3773}}</ref> as well as cyclic haliranium ions, fluorine was not believed to form fluoronium ions of type R–{{overset|+|F}}–R until the recent characterization of a fluoronium ion locked in a designed cage structure by Lectka and coworkers.<ref>{{Cite journal|last1=Pitts|first1=Cody Ross|last2=Holl|first2=Maxwell Gargiulo|last3=Lectka|first3=Thomas|date=2018-02-12|title=Spectroscopic Characterization of a [C−F−C]<sup>+</sup> Fluoronium Ion in Solution|journal=Angewandte Chemie International Edition|language=en|volume=57|issue=7|pages=1924–1927|doi=10.1002/anie.201712021|pmid=29316122|doi-access=}}</ref> Recent solvolysis experiments and NMR spectroscopic studies on a metastable [C–F–C]<sup>+</sup> fluoronium ion strongly support the [[Coordination number|dicoordinated]] fluoronium structure over the alternative rapidly equilibrating classical carbocation. Definitive structural proof of the symmetrical [C–F–C]<sup>+</sup> was reported by Riedel, Lectka, and coworkers by single crystal X-ray diffraction analysis. Besides its synthesis and crystallographic characterization as the [Sb<sub>2</sub>F<sub>11</sub>]<sup>−</sup> salt, vibrational spectra could be recorded and a detailed analysis concerning the nature of the bonding situation in this fluoronium ion and its heavier halonium homologues was reported.<ref>{{Cite journal|last1=Hoffmann|first1=Kurt F.|last2=Wiesner|first2=Anja|last3=Müller|first3=Carsten|last4=Steinhauer|first4=Simon|last5=Beckers|first5=Helmut|last6=Kazim|first6=Muhammad|last7=Pitts|first7=Cody Ross|last8=Lectka|first8=Thomas|last9=Riedel|first9=Sebastian|date=2021-09-06|title=Structural proof of a [C–F–C]+ fluoronium cation|journal=Nature Communications|language=en|volume=12|issue=1|pages=5275|doi=10.1038/s41467-021-25592-6|pmid=34489464 |pmc=8421340 |issn=2041-1723}}</ref> |
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:HF + H<sup>+</sup> → H<sub>2</sub>F<sup>+</sup> |
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or |
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:3HF {{unicode|⇌}} H<sub>2</sub>F<sup>+</sup> + [[Bifluoride|{{chem|HF|2|-}}]] |
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The fluoronium ion is isoelectronic with [[Properties of water|water]] and the [[Sodium amide|amide ion]]. |
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Whereas stable organic structures containing other [[halonium ion]]s have been known since 1970,<ref>{{cite journal | title = Friedel-Crafts chemistry. V. Isolation, carbon-13 nuclear magnetic resonance, and laser Raman spectroscopic study of dimethylhalonium fluoroantimonates | author = [[George A. Olah]], John R. DeMember | journal = [[J. Am. Chem. Soc.]] | doi = 10.1021/ja00706a058 | year = 1970 | volume = 92 | pages = 718 | issue = 3}}</ref> a fluoronium analog was not known until 2013 and even then only as an unstable short-lived entity.<ref>{{cite journal |volume= 91 |issue= 14 |page= 36 | title= Concentrates: Fluorine’s Positive Side Revealed |first1= Stephen K. |last1= Ritter |journal= Chemical & Engineering News}}</ref> |
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The kinetic instability of the fluoronium ion is responsible for the extreme acidity of [[fluoroantimonic acid]]. The [[antimony pentafluoride]] molecule sequesters the fluoride ion produced by the homoassociation of hydrogen fluoride, leaving the fluoronium ion unable to revert to the more stable neutral hydrogen fluoride. |
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== References == |
== References == |
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[[File:Lectka-fluoronium.png|thumb|A C<sub>s</sub>-symmetrical fluoronium ion characterized by Lectka and coworkers]] |
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{{reflist}} |
{{reflist}} |
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[[Category:Cations]] |
[[Category:Cations]] |
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[[Category:Fluorine compounds]] |
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[[Category:Hydrogen compounds]] |
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{{chem-stub}} |
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Latest revision as of 11:32, 3 December 2023
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| Names | |||
|---|---|---|---|
| IUPAC name
Fluoronium
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| Systematic IUPAC name
Fluoranium | |||
| Identifiers | |||
3D model (JSmol)
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| ChEBI | |||
| ChemSpider | |||
CompTox Dashboard (EPA)
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| Properties | |||
| H2F+ | |||
| Molar mass | 21.01374 g mol−1 | ||
| Conjugate base | Hydrogen fluoride | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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The fluoronium ion is an inorganic cation with the chemical formula H
2F+
. It is one of the cations found in fluoroantimonic acid.[1] The structure of the salt with the Sb
2F−
11 anion, has been determined.[2][3] The fluoronium ion is isoelectronic with the water molecule and the azanide ion.
The term can also refer to organyl substituted species of type H––R, R––R, or R2C=F+. In contrast to the heavier halogens, which have long been known to form open-chain halonium ions (such as [Me2Cl]+[Al(OTeF5)4]–)[4] as well as cyclic haliranium ions, fluorine was not believed to form fluoronium ions of type R––R until the recent characterization of a fluoronium ion locked in a designed cage structure by Lectka and coworkers.[5] Recent solvolysis experiments and NMR spectroscopic studies on a metastable [C–F–C]+ fluoronium ion strongly support the dicoordinated fluoronium structure over the alternative rapidly equilibrating classical carbocation. Definitive structural proof of the symmetrical [C–F–C]+ was reported by Riedel, Lectka, and coworkers by single crystal X-ray diffraction analysis. Besides its synthesis and crystallographic characterization as the [Sb2F11]− salt, vibrational spectra could be recorded and a detailed analysis concerning the nature of the bonding situation in this fluoronium ion and its heavier halonium homologues was reported.[6]
References
[edit]
- ^ Esteves, Pierre M.; Ramírez-Solís, Alejandro; Mota, Claudio J. A. (March 2002). "The Nature of Superacid Electrophilic Species in HF/SbF5: A Density Functional Theory Study". Journal of the American Chemical Society. 124 (11): 2672–2677. doi:10.1021/ja011151k. ISSN 0002-7863. PMID 11890818.
- ^ Mootz, Dietrich; Bartmann, Klemens (1988). "The Fluoronium Ions H2F+ and H
3F+
2: Characterization by Crystal Structure Analysis". Angewandte Chemie. 27 (3): 391–392. doi:10.1002/anie.198803911. - ^ Diercksen, G. H. F.; von Niessen, W.; Kraemer, W. P. (1973). "SCF LCGO MO studies on the fluoronium ion FH+
2 and its hydrogen bonding interaction with hydrogen fluoride FH". Theoretical Chemistry Accounts: Theory, Computation, and Modeling. 31 (3): 205–214. doi:10.1007/BF00526510. S2CID 98637994. - ^ Hämmerling, Sebastian; Thiele, Günther; Steinhauer, Simon; Beckers, Helmut; Müller, Carsten; Riedel, Sebastian (2019). "A Very Strong Methylation Agent: [Me2Cl][Al(OTeF5)4]". Angewandte Chemie International Edition. 58 (29): 9807–9810. doi:10.1002/anie.201904007. ISSN 1521-3773. PMID 31050103. S2CID 143434865.
- ^ Pitts, Cody Ross; Holl, Maxwell Gargiulo; Lectka, Thomas (2018-02-12). "Spectroscopic Characterization of a [C−F−C]+ Fluoronium Ion in Solution". Angewandte Chemie International Edition. 57 (7): 1924–1927. doi:10.1002/anie.201712021. PMID 29316122.
- ^ Hoffmann, Kurt F.; Wiesner, Anja; Müller, Carsten; Steinhauer, Simon; Beckers, Helmut; Kazim, Muhammad; Pitts, Cody Ross; Lectka, Thomas; Riedel, Sebastian (2021-09-06). "Structural proof of a [C–F–C]+ fluoronium cation". Nature Communications. 12 (1): 5275. doi:10.1038/s41467-021-25592-6. ISSN 2041-1723. PMC 8421340. PMID 34489464.
