From Divalent to Pentavalent Iron Imido Complexes and an Fe(V) Nitride via N-C Bond Cleavage

As key intermediates in metal-catalyzed nitrogen-transfer chemistry, terminal imido complexes of iron have attracted significant attention for a long time. In search of versatile model compounds, the recently developed second-generation N-anchored tris-NHC chelating ligand -[2-(3-mesityl-imidazole-2-ylidene)-methyl]amine (TIMMN^Mes) was utilized to synthesize and compare two series of mid- to high-valent iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate en route to an isolable Fe(V) nitrido complex. The chemistry toward the iron adamantyl imides was achieved by reacting the Fe(I) precursor [(TIMMN^Mes)Fe^I(N₂)]⁺ (1) with 1-adamantyl azide to yield the corresponding trivalent iron imide. Stepwise chemical reduction and oxidation lead to the isostructural series of low-spin [(TIMMN^Mes)Fe(NAd)]^0,1+,2+,3+ (2-5) in oxidation states II to V. The Fe(V) imide [(TIMMN^Mes)Fe(NAd)]³⁺ (5) is unstable under ambient conditions and converts to the air-stable nitride [(TIMMN^Mes)Fe^V(N)]²⁺ (6) via N-C bond cleavage. The stability of the pentavalent imide can be increased by derivatizing the nitride [(TIMMN^Mes)Fe^IV(N)]⁺ (7) with an ethyl group using the triethyloxonium salt Et₃OPF₆. This gives access to the analogous series of ethyl imides [(TIMMN^Mes)Fe(NEt)]^0,1+,2+,3+ (2-5), including the stable Fe(V) ethyl imide. Iron imido complexes exist in a manifold of different electronic structures, ultimately controlling their diverse reactivities. Accordingly, these complexes were characterized by single-crystal X-ray diffraction analyses, SQUID magnetization, and electrochemical methods, as well as ⁵⁷Fe Mössbauer, IR vibrational, UV/vis electronic absorption, multinuclear NMR, X-band EPR, and X-ray absorption spectroscopy. Our studies are complemented with quantum chemical calculations, thus providing further insight into the electronic structures of all complexes.