Nitrenium ion: Difference between revisions
Content deleted Content added
shameless plug? |
No edit summary |
||
| Line 1: | Line 1: | ||
{{About|the positive ions|other compounds with the formula NH<sub>2</sub> but different charges|amino radical|and|azanide}} |
{{About|the positive ions|other compounds with the formula NH<sub>2</sub> but different charges|amino radical|and|azanide}} |
||
A '''nitrenium ion''' (also called: '''aminylium ion''') in [[organic chemistry]] is a [[reactive intermediate]] based on [[nitrogen]] with both an electron [[lone pair]] and a [[cation|positive charge]] and with two substituents (R<sub>2</sub>N<sup>+</sup>).<ref>Reactive Intermediate Chemistry |
A '''nitrenium ion''' (also called: '''aminylium ion''') in [[organic chemistry]] is a [[reactive intermediate]] based on [[nitrogen]] with both an electron [[lone pair]] and a [[cation|positive charge]] and with two substituents (R<sub>2</sub>N<sup>+</sup>).<ref>{{cite book|title=Reactive Intermediate Chemistry|editor1-last=Moss|editor1-first=Robert A.|editor2-last=Platz|editor2-first=Matthew S.|editor3-last=Jones|editor3-first=Maitland, Jr|publisher=Wiley|date=2004|isbn=9780471233244}}{{page needed}}</ref><ref>{{GoldBookRef|file=N04146|title=nitrenium ions}}</ref> Nitrenium ions are [[isoelectronic]] with [[carbene]]s, and can exist in either a singlet or a [[triplet state]]. The parent nitrenium ion, {{chem2|NH2+}}, is a ground state triplet species with a gap of {{cvt|30|kcal/mol|kJ/mol}} to the lowest energy singlet state. Conversely, most arylnitrenium ions are ground state singlets. Certain substituted arylnitrenium ions can be ground state triplets, however. |
||
Aryl nitrenium ions are currently investigated because of their involvement in certain [[DNA]] damaging processes. These intermediates can have microsecond or longer lifetimes in water.<ref> |
Aryl nitrenium ions are currently investigated because of their involvement in certain [[DNA]] damaging processes. These intermediates can have microsecond or longer lifetimes in water.<ref>{{cite journal|title=Reaction of aromatic azides with strong acids: Formation of fused nitrogen heterocycles and arylamines|first1=Marcia|last1=de Carvalho|first2=Ana E. P. M.|last2=Sorrilha|first3=J. Augusto R.|last3=Rodrigues|journal=Journal of the Brazilian Chemical Society|volume=10|issue=5|page=415–420|date=1999|url=http://www.scielo.br/pdf/jbchs/v10n5/a12v10n5.pdf|doi=https://doi.org/10.1590/S0103-50531999000500012 }}</ref> They can also be exploited for useful synthetic processes. |
||
Fused Nitrogen Heterocycles and Arylamines'' Marcia de Carvalho, Ana E.P.M. Sorrilha, and J. Augusto R. Rodrigues J. Braz. Chem. Soc., Vol. 10, No. 5, 415-420, '''1999'''. [http://www.scielo.br/pdf/jbchs/v10n5/a12v10n5.pdf link]</ref> They can also be exploited for useful synthetic processes. |
|||
Nitrenium ions are also intermediates in organic reactions; for instance, the [[Bamberger rearrangement]]. They can also act as [[electrophile]]s in [[electrophilic aromatic substitution]].<ref> |
Nitrenium ions are also intermediates in organic reactions; for instance, the [[Bamberger rearrangement]]. They can also act as [[electrophile]]s in [[electrophilic aromatic substitution]].<ref>{{cite journal|title=Microwave-assisted generation of carbazolyl nitrenium cation|first=Dariusz|last=Bogdał|journal=[[ARKIVOC]]|volume=2001|date=2001|issue=6|page=109–115|doi=10.3998/ark.5550190.0002.611}}</ref> |
||
Phenylnitrenium ion reaction with [[guanine]], DFT energies for 22 isomeric adducts.<ref>Parks |
Phenylnitrenium ion reaction with [[guanine]], DFT energies for 22 isomeric adducts.{{clarify}}<ref>{{cite journal|last1=Parks|first1=J. M.|last2=Ford|first2=G. P.|last3=Cramer|first3=C. J.|title=Quantum chemical characterization of the reactions of guanine with the phenylnitrenium ion |
||
|journal=Journal of Organic Chemistry|volume=66|issue=26|page=8997–9004|date=2001|pmid=11749633|doi=10.1021/jo016066+}}</ref> |
|||
The term '''imidonium ion''' with the same meaning, is now obsolete. |
The term '''imidonium ion''' with the same meaning, is now obsolete. |
||
==See also== |
==See also== |
||
* The related neutral [[nitrene]]s |
* The related neutral [[nitrene]]s R–N''':''' |
||
==References== |
==References== |
||
Revision as of 18:44, 17 September 2020
A nitrenium ion (also called: aminylium ion) in organic chemistry is a reactive intermediate based on nitrogen with both an electron lone pair and a positive charge and with two substituents (R2N+).[1][2] Nitrenium ions are isoelectronic with carbenes, and can exist in either a singlet or a triplet state. The parent nitrenium ion, NH+2, is a ground state triplet species with a gap of 30 kcal/mol (130 kJ/mol) to the lowest energy singlet state. Conversely, most arylnitrenium ions are ground state singlets. Certain substituted arylnitrenium ions can be ground state triplets, however.
Aryl nitrenium ions are currently investigated because of their involvement in certain DNA damaging processes. These intermediates can have microsecond or longer lifetimes in water.[3] They can also be exploited for useful synthetic processes.
Nitrenium ions are also intermediates in organic reactions; for instance, the Bamberger rearrangement. They can also act as electrophiles in electrophilic aromatic substitution.[4]
Phenylnitrenium ion reaction with guanine, DFT energies for 22 isomeric adducts.[clarification needed][5]
The term imidonium ion with the same meaning, is now obsolete.
See also
- The related neutral nitrenes R–N:
References
- ^ Moss, Robert A.; Platz, Matthew S.; Jones, Maitland, Jr, eds. (2004). Reactive Intermediate Chemistry. Wiley. ISBN 9780471233244.
{{cite book}}: CS1 maint: multiple names: editors list (link)[page needed] - ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "nitrenium ions". doi:10.1351/goldbook.N04146
- ^ de Carvalho, Marcia; Sorrilha, Ana E. P. M.; Rodrigues, J. Augusto R. (1999). "Reaction of aromatic azides with strong acids: Formation of fused nitrogen heterocycles and arylamines" (PDF). Journal of the Brazilian Chemical Society. 10 (5): 415–420. doi:https://doi.org/10.1590/S0103-50531999000500012.
{{cite journal}}: Check|doi=value (help); External link in|doi= - ^ Bogdał, Dariusz (2001). "Microwave-assisted generation of carbazolyl nitrenium cation". ARKIVOC. 2001 (6): 109–115. doi:10.3998/ark.5550190.0002.611.
- ^ Parks, J. M.; Ford, G. P.; Cramer, C. J. (2001). "Quantum chemical characterization of the reactions of guanine with the phenylnitrenium ion". Journal of Organic Chemistry. 66 (26): 8997–9004. doi:10.1021/jo016066+. PMID 11749633.