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