Transient resonance Raman and density functional theory investigation of the 2-fluorenylnitrenium ion.
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.
Zhu
P
P
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong S. A. R., P. R. China.
Ong
S Y
SY
Chan
P Y
PY
Leung
K H
KH
Phillips
D L
DL