Direct Observation of an Imidoylnitrene: Photochemical Formation of PhC(=NMe)−N and Me−N from 1‐Methyl‐5‐phenyltetrazole

The imidoylnitrene 8, N‐methyl‐C‐phenylimidoylnitrene, has been generated by laser photolysis of 1‐methyl‐5‐phenyltetrazole 6 at 5 K and characterized by its ESR spectrum (|D/hc|=0.9602, |E/hc|=0.0144 cm−1). In addition, the triplet excited states of 6 and of 2‐methyl‐5‐phenyltetrazole 11 were also observed by ESR spectroscopy in the 5 K matrices (6: |D/hc|=0.123 cm−1, E/hc=0.0065 cm−1, 11: |D/hc|=0.126 cm−1, |E/hc|=0.0056 cm−1). The imidoylnitrene 8 is unstable both thermally (disappearing at 80 K) and photochemically (disappearing on continued irradiation at 266 nm). Methyl(phenyl)carbodiimide is the end product of photolysis.