Characterization of Smith's nitrene and 1-phenyl-3-(α-cyano)benzylidenetriazene with theoretical, NMR, and flash photolytic methods

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Doubly enriched (13C, 15N) 1-phenyl-3-(α-cyano)benzylidenetriazene, Ph-N*=N-N=C(C*≡N)-Ph, did not show 13C-15N splittings in the NMR spectra in solution that would be expected from the presence of a cyclic nitrene in reversible equilibrium, a theory proposed in 1964 by Smith, Krbechek, and Resemann to explain its chemical behavior. Molecular orbital calculations at the 6-31G* level on the core structures (Ph replaced by H) also indicated substantially greater stability for the open-chain compound. Flash photolysis (337 nm) of 1,4-diphenyl-5-azido-1,2,3-triazole in solution led to the open-chain triazene within about 20 ns but with no observable transient absorbing species.

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Journal of Physical Chemistry A