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 Me 3 C – NN – Ar (Arphenyl, p ‐tolyl, p ‐CH 3 OC 6 H 4 ) produces in the first step ortho ‐metallated complexes of the type Me 3 C – N – N(H)RC 6 H 3 Fe(CO) 3 Fe(CO) 3 ( 2a – c , RH, Me, MeO). In a thermal consecutive step these intermediates undergo an o ‐semidine rearrangement to Me 3 C – NFe(CO) 3 – Fe(CO) 3 N(H)RC 6 H 3 ( 1a – c ). The structure of 1a has been elucidated by X‐ray structure analysis. Dynamic 13 C‐NMR spectra indicate restricted rotation of the Me 3 C group and hindered carbonyl scrambling for the latter and former complexes, respectively.