How Do Different Fluorine Substitution Patterns Affect the Electronic State Energies of Phenylnitrene?

Smith, B. A.; Cramer, C. J.
J. Am. Chem. Soc. 1996, 118, 5490.

Ab initio density functional and molecular orbital calculations indicate that fluorine substitution at either the ortho or para positions of phenylnitrene polarizes the pi system in a manner that stabilizes the 1¹A₁ state and destabilizes the 2¹A₁ state relative to the triplet. To the extent that 2¹A₁ state character is reflected in the transition state for ring opening, this rationalizes the increased barrier for these substituted phenylnitrenes to engage in that process, and contributes to their utility as photoaffinity labeling agents. This effect is absent for meta-substitution of fluorine since the pi system is not polarized.

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