title: Time-resolved resonance Raman investigation of the 2-fluorenylnitrenium ion reactions with C8 guanosine derivatives.
abstract: A nanosecond time-resolved resonance Raman (ns-TR3) spectroscopic study of the reactions of the 2-fluorenylnitrenium ion with several C8-substituted guanosine derivatives is reported. The TR3 spectra show that the 2-fluorenylnitrenium ion reacts with the C8-substituted guanosine derivatives (C8-methylguanosine and C8-bromoguanosine) to produce C8 intermediates with the methyl and bromine moieties still attached to the intermediate species at the C8 position. The C8-bromoguanosine species was observed to be less reactive toward the 2-fluorenylnitrenium ion compared to the guanosine and C8-methylguanosine species. Comparison of the TR3 spectra to the results obtained from density functional theory calculations was used to characterize the C8 intermediates observed to learn more about their structure and properties. The implications of these results for the chemical reactivity of arylnitrenium ions toward substituted guanosine derivatives are briefly discussed.
authors.affiliation: Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, PR China.
authors.forename: Jiadan
authors.initials: J
authors.lastname: Xue
authors.forename: Pik Ying
authors.initials: PY
authors.lastname: Chan
authors.forename: Yong
authors.initials: Y
authors.lastname: Du
authors.forename: Zhen
authors.initials: Z
authors.lastname: Guo
authors.forename: Cecilia Wan Ying
authors.initials: CW
authors.lastname: Chung
authors.forename: Patrick H
authors.initials: PH
authors.lastname: Toy
authors.forename: David Lee
authors.initials: DL
authors.lastname: Phillips
mesh_terms: D005449:Fluorenes / Q000737:chemistry*; D006151:Guanosine / Q000031:analogs & derivatives* / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008968:Molecular Conformation; D010782:Photolysis; D012015:Reference Standards; D013059:Spectrum Analysis, Raman / Q000379:methods* / Q000592:standards; D013237:Stereoisomerism; D013997:Time Factors
chemical_list: C525234:2-fluorenylnitrenium; D005449:Fluorenes; D007477:Ions; D006151:Guanosine