Deciphering Iron‐Catalyzed C−H Amination with Organic Azides: N 2 Cleavage from a Stable Organoazide Complex

Stroek, Wowa; Keilwerth, Martin; Malaspina, Lorraine A.; Grabowsky, Simon; Meyer, Karsten; Albrecht, Martin (2024). Deciphering Iron‐Catalyzed C−H Amination with Organic Azides: N 2 Cleavage from a Stable Organoazide Complex. Chemistry – A European Journal, 30(4) European Chemical Societies Publishing 10.1002/chem.202303410

[img] Text
107_Stroek2024_ChemEurJ.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (2MB) | Request a copy

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, α-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 α-N coordinated organoazide complex from [Fe(N(SiMe3)2)2] and AdN3 (Ad=1-adamantyl) and its crystallographic, IR, NMR and zero-field 57Fe Mössbauer spectroscopic characterization. These analyses revealed that the organoazide is in fast equilibrium between the free and coordinated state (Keq=62). Photo-crystallography experiments showed gradual dissociation of N2, 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 N2, 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 1H NMR spectroscopy indicates the transient formation of the imido/nitrene intermediate, which was supported by Mössbauer spectroscopy in frozen solution.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Stroek, Vladimir Vladimirovich, Malaspina, Lorraine, Grabowsky, Simon, Albrecht, Martin


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
000 Computer science, knowledge & systems




European Chemical Societies Publishing




Simon Grabowsky

Date Deposited:

14 Mar 2024 11:41

Last Modified:

14 Mar 2024 11:41

Publisher DOI:





Actions (login required)

Edit item Edit item
Provide Feedback