Phenylnitrene Radical Cation and Its Isomers from Tetrazoles, Nitrile Imines, Indazole, and Benzimidazole.

Phenylnitrene radical cations m/ z 91, C6H5N, 8a•+ are observed in the mass spectra of 1-, 2-, and 5-phenyltetrazoles, even though no C-N bond is present in 5-phenyltetrazole. Calculations at the B3LYP/6-311G(d,p) level of theory indicate that initial formation of the C-phenylimidoylnitrene 13•+ and/or benzonitrile imine radical cation 19•+ from 1 H- and 2 H-5-phenyltetrazoles 11 and 12 is followed by isomerizations of 13•+ to the phenylcyanamide ion 15•+ over a low barrier. A cyclization of imidoylnitrene ion 13•+ onto the benzene ring offers alternate, very facile routes to the phenylnitrene ion 8a•+ and the phenylcarbodiimide ion 14•+ via the azabicyclooctadienimine 16•+. Eliminations of HNC or HCN from 14•+ and 15•+ again yield the phenylnitrene radical cation 8a•+. A direct 1,3-H shift isomerizing phenylcarbodiimide ion 14•+ to the phenylcyanamide ion 15•+ requires a very high activation energy of 114 kcal/mol, and this reaction needs not be involved. The benzonitrile imine -3-phenyl-1 H-diazirine-phenylimidoylnitrene-phenylcarbodiimide/phenylcyanamide rearrangement has parallels in thermal and photochemical processes, but the facile cyclization of imidoylnitrene 13•+ to azabicyclooctadienimine 16•+ is facilitated by the positive charge making the nitrene more electrophilic. Furthermore, the benzonitrile imine radical cation 19•+ can cyclize to indazole 24•+, and a series of intramolecular rearrangements via hydrogen shifts, ring-openings and ring closures allow the interconversion of numerous ions of composition C7H6N2•+, including 19•+, 24•+, the benzimidazole ion 38•+ and o-aminobenzonitrile ion 40•+, all of which can eliminate either HCN or HNC to yield the C6H5N•+ ions of phenylnitrene, 8a•+, and/or iminocyclohexadienylidene, 34•+. Moreover, benzonitrile imine 19•+ can behave like a benzylic carbenium ion, undergoing a novel ring expansion to cycloheptatetraenyldiazene 45•+. The N-phenylnitrile imine ion 2d•+ derived from 2-phenyltetrazole 1d cleaves efficiently to the phenylnitrene ion 8a•+ but may also cyclize to the indazole ion 24•+. The N-phenylimidoylnitrene 59•+ derived from 1-phenyltetrazole 5d undergoes facile isomerization to the phenylcyanamide ion 15•+ and hence phenylnitrene radical cation 8a•+.