title: Transient resonance Raman and density functional theory investigation of the 2-fluorenylnitrenium ion.
abstract: We report a transient resonance Raman spectrum for the 2-fluorenylnitrenium ion obtained after photolysis of 2-azidofluorene. The 10 experimental Raman band frequencies of the transient spectrum show very good agreement with the computed frequencies from BPW91/cc-PVDZ density functional theory calculations for the 2-fluorenylnitrenium ion. Our results confirm the assignment of the approximately 460 nm transient absorption band formed after photolysis of 2-azidofluorene in water/acetonitrile or water solution to the singlet ground electronic state 2-fluorenylnitrenium ion. Our study indicates the 2-fluorenylnitrenium has a large degree of iminocyclohexadienyl cation character with significant delocalization of the charge over both phenyl rings of the fluorene moiety. We compare our results for the 2-fluoreneylnitrenium ion to those previously reported for several other arylnitrenium ions.
authors.affiliation: Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong S. A. R., P. R. China.
authors.forename: P
authors.initials: P
authors.lastname: Zhu
authors.forename: S Y
authors.initials: SY
authors.lastname: Ong
authors.forename: P Y
authors.initials: PY
authors.lastname: Chan
authors.forename: K H
authors.initials: KH
authors.lastname: Leung
authors.forename: D L
authors.initials: DL
authors.lastname: Phillips