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Article: Direct observation of the 2-fluorenylnitrene and 4-methoxyphenylnitrene reactions with water using picosecond kerr-gated time-resolved resonance raman spectroscopy

TitleDirect observation of the 2-fluorenylnitrene and 4-methoxyphenylnitrene reactions with water using picosecond kerr-gated time-resolved resonance raman spectroscopy
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfk
Citation
Journal Of Physical Chemistry B, 2004, v. 108 n. 49, p. 19068-19075 How to Cite?
AbstractA picosecond Kerr-gated time-resolved resonance Raman examination of the 2-fluorenylnitrene and 4-methoxyphenylnitrene reactions with water to form the singlet 2-fluorenylnitrenium and 4-methoxyphenylnitrenium ions, respectively, is given. Photolysis of 2-fluorenyl azide and 4-methoxyphenyl azide in mixed water/acetonitrile solvents both led to formation of transient species within a few picoseconds, and these were tentatively assigned to the 2-fluorenylnitrene and 4-methoxyphenylnitrene species, respectively. These arylnitrenes were observed to directly react with water to produce their respective singlet arylnitrenium ions. The decay of the 4-methoxyphenylnitrene species and its accompanying growth of the 4-methoxyphenylnitrenium ion were found to be much faster than the decay of the 2-fluorenylnitrene and its accompanying growth of its 2-fluorenylnitrenium ion, indicating these two different arylnitrenes have noticeably different chemical reactivity toward water. The 4- methoxyphenylnitrene species spectra displayed noticeable changes in its time-resolved Raman spectra as the solvent system is changed from pure acetonitrile to a mixed water/ acetonitrile solvent whereas the 2-fluorenylnitrene spectra displayed very little if any change. These results suggest hydrogen bonding with the methoxy moiety.
Persistent Identifierhttp://hdl.handle.net/10722/69615
ISSN
2015 Impact Factor: 3.187
2015 SCImago Journal Rankings: 1.414
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorChan, PYen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:15:17Z-
dc.date.available2010-09-06T06:15:17Z-
dc.date.issued2004en_HK
dc.identifier.citationJournal Of Physical Chemistry B, 2004, v. 108 n. 49, p. 19068-19075en_HK
dc.identifier.issn1520-6106en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69615-
dc.description.abstractA picosecond Kerr-gated time-resolved resonance Raman examination of the 2-fluorenylnitrene and 4-methoxyphenylnitrene reactions with water to form the singlet 2-fluorenylnitrenium and 4-methoxyphenylnitrenium ions, respectively, is given. Photolysis of 2-fluorenyl azide and 4-methoxyphenyl azide in mixed water/acetonitrile solvents both led to formation of transient species within a few picoseconds, and these were tentatively assigned to the 2-fluorenylnitrene and 4-methoxyphenylnitrene species, respectively. These arylnitrenes were observed to directly react with water to produce their respective singlet arylnitrenium ions. The decay of the 4-methoxyphenylnitrene species and its accompanying growth of the 4-methoxyphenylnitrenium ion were found to be much faster than the decay of the 2-fluorenylnitrene and its accompanying growth of its 2-fluorenylnitrenium ion, indicating these two different arylnitrenes have noticeably different chemical reactivity toward water. The 4- methoxyphenylnitrene species spectra displayed noticeable changes in its time-resolved Raman spectra as the solvent system is changed from pure acetonitrile to a mixed water/ acetonitrile solvent whereas the 2-fluorenylnitrene spectra displayed very little if any change. These results suggest hydrogen bonding with the methoxy moiety.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfken_HK
dc.relation.ispartofJournal of Physical Chemistry Ben_HK
dc.titleDirect observation of the 2-fluorenylnitrene and 4-methoxyphenylnitrene reactions with water using picosecond kerr-gated time-resolved resonance raman spectroscopyen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1520-6106&volume=108&spage=19068&epage=19075&date=2004&atitle=Direct+observation+of+the+2-fluorenylnitrene+and+4-methoxyphenylnitrene+reactions+with+water+using+picosecond+Kerr-gated+time-resolved+resonance+Raman+spectroscopyen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jp0467292en_HK
dc.identifier.scopuseid_2-s2.0-10844240622en_HK
dc.identifier.hkuros98485en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-10844240622&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume108en_HK
dc.identifier.issue49en_HK
dc.identifier.spage19068en_HK
dc.identifier.epage19075en_HK
dc.identifier.isiWOS:000225548700041-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridKwok, WM=7103129332en_HK
dc.identifier.scopusauthoridChan, PY=7403497922en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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