Deciphering Iron-Catalyzed C-H Amination with Organic Azides: N2 Cleavage from a Stable Organoazide Complex

Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. En route to C-H amination, complexes with organic azides are critical precursors towards the reactive nitrene intermediate. Despite their relevance, alpha-N coordinated organoazide complexes are scarce in general, and elusive with iron, although iron complexes are by far the most active catalysts for C-H amination with organoazides. Herein, we report the synthesis of a stable iron alpha-N coordinated organoazide complex from [Fe(N(SiMe3)(2))(2)] and AdN(3) (Ad=1-adamantyl) and its crystallographic, IR, NMR and zero-field Fe-57 M & ouml;ssbauer spectroscopic characterization. These analyses revealed that the organoazide is in fast equilibrium between the free and coordinated state (K-eq=62). Photo-crystallography experiments showed gradual dissociation of N-2, which imparted an Fe-N bond shortening and correspond to structural snapshots of the formation of an iron imido/nitrene complex. Reactivity of the organoazide complex in solution showed complete loss of N-2, and subsequent formation of a C-H aminated product via nitrene insertion into a C-H bond of the N(SiMe3)(2) ligand. Monitoring this reaction by H-1 NMR spectroscopy indicates the transient formation of the imido/nitrene intermediate, which was supported by M & ouml;ssbauer spectroscopy in frozen solution.

Automated summary

Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. This study reports the synthesis of a stable iron alpha-N coordinated organoazide complex and reveals its reaction mechanism in solution.