| Revision as of 09:44, 24 November 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 462235331 of page Triphenylmethyl_radical for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 17:52, 25 November 2024 edit 5.178.188.143 (talk)No edit summaryTag: Visual edit |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{Chembox |
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| ImageFile = Triphenylmethylradical.png |
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|verifiedrevid = 462238281 |
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| ImageFile_Ref = {{chemboximage|correct|??}} |
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|ImageFile = Triphenylmethyl radical.svg |
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| ImageName = Kekulé, skeletal formula of the triphenylmethyl radical |
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|ImageSize = 175 |
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| Section1 = {{Chembox Identifiers |
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|ImageFile_Ref = {{chemboximage|correct|??}} |
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| ChemSpiderID = 10627185 |
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|ImageName = Kekulé, skeletal formula of the triphenylmethyl radical |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ImageFile1 = Triphenylmethyl radical ball.png |
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| SMILES = c1ccc(cc1)(c1ccccc1)c1ccccc1 |
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|ImageAlt1 = Ball-and-stick model of the triphenylmethyl radical |
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| SMILES1 = C1=CC=C(C=C1)(C1=CC=CC=C1)C1=CC=CC=C1 |
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|PIN = Triphenylmethyl |
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| StdInChI = 1S/C19H15/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18/h1-15H |
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|Section1={{Chembox Identifiers |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|CASNo = 2216-49-1 |
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| StdInChIKey = OHSJPLSEQNCRLW-UHFFFAOYSA-N |
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|CASNo_Ref = {{Cascite|changed|CAS}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|ChemSpiderID = 10627185 |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|PubChem = 5374035 |
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|SMILES = c1ccc(cc1)(c1ccccc1)c1ccccc1 |
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|SMILES1 = C1=CC=C(C=C1)(C1=CC=CC=C1)C1=CC=CC=C1 |
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|StdInChI = 1S/C19H15/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18/h1-15H |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey = OHSJPLSEQNCRLW-UHFFFAOYSA-N |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C = 19 |
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|C=19 | H=15 |
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| H = 15 |
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| ExactMass = 243.117375480 g mol<sup>-1</sup> |
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The '''triphenylmethyl radical''' (often shortened to '''trityl radical''' after 1927 suggestion by ] et al.<ref>{{Cite journal |last=Helferich |first=B. |last2=Bredereck |first2=H. |last3=Schneidmüller |first3=A. |date=1927 |title=Acylwanderung an partiell acylierten Methyl‐glucosiden |url=https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/jlac.19274580108 |journal=Justus Liebigs Annalen der Chemie |language=de |volume=458 |issue=1 |pages=111–116 |doi=10.1002/jlac.19274580108 |issn=0075-4617}}</ref>) is an ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>C. It is a ]. It was the first ] ever to be described in ]. Because of its accessibility, the trityl radical has been heavily exploited.<ref>{{cite book |doi=10.1002/9780470666975.ch1|chapter=Triarylmethyl and Related Radicals|title=Stable Radicals|year=2010|last1=Tidwell|first1=Thomas T.|pages=1–31|isbn=9780470666975}}</ref> |
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== Preparation and properties == |
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The triphenylmethyl radical can be prepared by ] of ] '''1''' by a metal like ] or ] in ] or ]. The radical '''2''' forms a ] with the ]-type ] '''3''' (]). In benzene the concentration of the radical is 2%.<ref>{{March6th}} </ref> |
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] |
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Solutions containing the radical are ]; when the temperature of the solution is raised, the yellow color becomes more intense as the equilibrium is shifted in favor of the radical rather than the colorless dimer, in accordance with ]. |
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The triphenylmethyl radical exhibits green ]. Further reaction of the quinoid dimer with another triphenylmethyl radical produces a quinoid radical that exhibits red photoluminescence.<ref name="Red photoluminescence">{{cite journal |doi=10.1070/MC2000v010n01ABEH001115 |title=Red photoluminescence in the synthesis of triphenylmethyl radicals by the Gomberg method |date=2000 |last1=Bulgakov |first1=Ramil G. |last2=Kuleshov |first2=Sergei P. |last3=Valiullina |first3=Zemfira S. |journal=Mendeleev Communications |volume=10 |pages=22–23 }}</ref> |
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When exposed to air, the radical rapidly oxidizes to the ], and the color of the solution changes from yellow to colorless. Likewise, the radical reacts with ] to triphenylmethyl iodide. |
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] |
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While the triphenyl radical itself forms a quinoid dimer, derivatives of the triphenyl radical with certain ] phenyl groups do form dimers with a ]-like structure. For example, the tris(3,5-di-''tert''-butylphenyl) radical dimerizes to give hexakis(3,5-di-''t''-butylphenyl)ethane, with a ] of 1.67 Å for the central carbon–carbon bond. Theoretical calculations on a very high level of theory indicate that ] between the ] groups create a potential minimum that is absent in the unsubstituted molecule.<ref>{{Citation|last=Lewars|first=Errol|title=Modeling Marvels|year=2008|chapter=8. Hexaphenylethane|publisher=Springer|bibcode=2008moma.book.....L}}</ref><ref>{{cite journal|last1=Grimme|first1=Stefan|last2=Schreiner|first2=Peter R.|year=2011|title=Steric crowding can stabilize a labile molecule: Solving the hexaphenylethane riddle|journal=Angewandte Chemie International Edition|volume=50|issue=52|pages=12639–12642|doi=10.1002/anie.201103615|pmid=22025456}}</ref> Other derivatives have been reported as the quinoid dimer <ref>{{cite journal|last1=Uchimura|first1=Y.|last2=Takeda|first2=T.|last3=Katoono|first3=R.|last4=Fujiwara|first4=K.|last5=Suzuki|first5=T.|date=2015|title=New Insights into the Hexaphenylethane Riddle: Formation of an α,''o''-Dimer.|journal=Angewandte Chemie International Edition|volume=54|issue=13|pages=4010–4013|doi=10.1002/anie.201500122|pmid=25704856}}</ref> |
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The class of tri]-methyl radicals have applications in the synthesis of organic ]s.<ref name="Organic magnet">{{cite journal |doi=10.1070/RC2006v075n10ABEH003621 |title=From the Gomberg radical to organic magnets |date=2006 |last1=Shishlov |first1=Nikolay M. |journal=Russian Chemical Reviews |volume=75 |issue=10 |pages=863–884 }}</ref> |
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== History == |
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The radical was discovered by ] in 1900 at the ].<ref>{{cite journal | title = An instance of trivalent carbon: triphenylmethyl | authorlink = Moses Gomberg|first=M. |last=Gomberg | journal = ] | year = 1900 | volume = 22 | issue = 11 | pages = 757–771 | doi = 10.1021/ja02049a006| url = https://zenodo.org/record/1428920}}</ref><ref>{{cite journal | title = On trivalent carbon|first=M. |last=Gomberg | journal = Journal of the American Chemical Society | year = 1901 | volume = 23 | issue = 7 | pages = 496–502 | doi = 10.1021/ja02033a015}} (Note: radical is also called a ''cadicle''.)</ref><ref>{{cite journal | title = On trivalent carbon |first=M. |last=Gomberg | journal = Journal of the American Chemical Society | year = 1902 | volume = 24 | issue = 7 | pages = 597–628 | doi = 10.1021/ja02021a001| url = https://zenodo.org/record/1428904}}</ref> He tried to prepare ] from triphenylmethyl chloride and zinc in benzene in a ] and found that the product, based on its behaviour towards iodine and oxygen, was far more reactive than anticipated. The discovered structure was used in the development of ] spectroscopy and confirmed by it.<ref>{{cite journal | title = Electron distribution in triphenylmethyl: Hyperfine structure of the paramagnetic resonance absorption of (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>C<sup>13*</sup>| first1= S. I. |last1=Weissman |first2=John C. |last2=Sowden | journal = ]| volume = 75 | issue = 2|year = 1953|pages = 503| doi = 10.1021/ja01098a522}}</ref><ref>{{cite journal | title = Electron spin resonance studies of substituted triphenylmethyl radicals | first1= J. |last1= Sinclair |first2= D.|last2= Kivelson | journal = Journal of the American Chemical Society| volume = 90 | issue = 19 |year = 1968|pages = 5074–5080 | doi = 10.1021/ja01021a004}}</ref><ref>{{cite web |url= http://www.chm.bris.ac.uk/motm/triphenylmethyl/tripesr1.html|title= ESR spectrum of the triphenylmethyl radical|last= |first= |date= |website= |publisher= School of Chemistry, University of Bristol|access-date= August 5, 2018}}</ref> The triphenylmethyl radical, and the larger class of triarylmethyl radicals, are called ''Gomberg radicals''.<ref name="Red photoluminescence"/><ref name="Organic magnet"/> |
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The correct ] structure for the dimer was suggested as early as 1904 but this structure was soon after abandoned by the scientific community in favor of hexaphenylethane ('''4''').<ref>{{cite journal | title = The hexaphenylethane riddle | first= J. M. |last=McBride | journal = ] | volume = 30 | issue = 14 | year = 1974 | pages = 2009–2022 | doi = 10.1016/S0040-4020(01)97332-6}}</ref> It subsequently took until 1968 for its rediscovery when researchers at the ] published ] data.<ref>{{cite journal | title = A new interpretation of the monomer–dimer equilibrium of triphenylmethyl- and alkyl-substituted-diphenyl methyl-radicals in solution | first1= H. |last1=Lankamp |first2=W. Th. |last2=Nauta |first3= C.|last3= MacLean | journal = ] | volume = 9 | issue = 2 |year = 1968 | pages = 249–254 | doi = 10.1016/S0040-4039(00)75598-5}}</ref> |
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==See also== |
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* ] |
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* ] |
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* ] |
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* ] |
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==References== |
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{{reflist|2}} |
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==External links== |
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* , June 1997 |
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] |
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] |