Übergangsmetallkomplexe von Diazenen, XXVII. Eisencarbonyl‐induzierte o‐Semidin‐Umlagerung von 1‐Alkyl‐2‐aryldiazenen

Iron Carbonyl Induced o‐Semidine Rearrangement of 1‐Alkyl‐2‐aryldiazenes Irradiation of pentacarbonyl iron in the presence of Me3C – NN – Ar (Arphenyl, p‐tolyl, p‐CH3OC6H4) produces in the first step ortho‐metallated complexes of the type Me3C – N – N(H)RC6H3Fe(CO)3Fe(CO)3 (2a–c, RH, Me, MeO). In a thermal consecutive step these intermediates undergo an o‐semidine rearrangement to Me3C – NFe(CO)3 – Fe(CO)3N(H)RC6H3 (1a–c). The structure of 1a has been elucidated by X‐ray structure analysis. Dynamic 13C‐NMR spectra indicate restricted rotation of the Me3C group and hindered carbonyl scrambling for the latter and former complexes, respectively.