Organometallic μ-Nitridodiiron Complexes in Oxidation States Ranging from (III/III) to (IV/IV)

Iron complexes with nitrido ligands are of interest as molecular analogues of key intermediates during N₂-to-NH₃ conversion in industrial or enzymatic processes. Dinuclear iron complexes with a bridging nitrido unit are mostly known in relatively high oxidation states (III/IV or IV/IV), originating from the decomposition of azidoiron precursors via high-valent Fe≡N intermediates. The use of a tetra-NHC macrocyclic scaffold ligand (NHC = N-heterocyclic carbene) has now allowed for the isolation of a series of organometallic μ-nitridodiiron complexes ranging from the mid-valent Fe^III-N-Fe^III (1) via mixed-valent Fe^III-N-Fe^IV (type 4) to the high-valent Fe^IV-N-Fe^IV (type 5) species that are interconverted at moderate potentials, accompanied by axial ligand binding at the Fe^IV sites. Magnetic measurements and electron paramagnetic resonance spectroscopy showed the homovalent complexes to be diamagnetic and the mixed-valent system to feature an S = 1/2 ground state due to very strong antiferromagnetic coupling. The bonding in the Fe-N-Fe moiety has been further probed by crystallographic structure determination, ⁵⁷Fe Mössbauer and UV-vis spectroscopies, as well as density functional theory computations, which revealed high covalency and nearly identical Fe-N distances across this redox series. The latter has been rationalized in terms of the nonbonding nature of the combination of Fe d atomic orbitals from which electrons are successively removed upon oxidation, and these redox processes are best described as being metal-centered. The tetra-NHC-ligated μ-nitridodiiron series complements a set of related complexes with single-atom μ-oxido and μ-phosphido bridges, but the Fe-N-Fe core exhibits a comparatively high stability over several oxidation states. This promises interesting applications in view of the manifold catalytic uses of μ-nitridodiiron complexes based on macrocyclic N-donor porphinato(2-) or phthalocyaninato(2-) ligands.