Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States

An isostructural series of Fe^II, Fe^III, and Fe^IV complexes [Fe(ImP)₂]^0/+/2+ utilizing the ImP 1,1'-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene) ligand, combining <i>N</i>-heterocyclic carbenes and cyclometalating functions, is presented. The strong donor motif stabilizes the high-valent Fe^IV oxidation state yet keeps the Fe^II oxidation state accessible from the parent Fe^III compound. Chemical oxidation of [Fe(ImP)₂]⁺ yields stable [Fe^IV(ImP)₂]²⁺. In contrast, [Fe^II(ImP)₂]⁰, obtained by reduction, is highly sensitive toward oxygen. Exhaustive ground state characterization by single-crystal X-ray diffraction, ¹H NMR, Mössbauer spectroscopy, temperature-dependent magnetic measurements, a combination of X-ray absorption near edge structure and valence-to-core, as well as core-to-core X-ray emission spectroscopy, complemented by detailed density functional theory (DFT) analysis, reveals that the three complexes [Fe(ImP)₂]^0/+/2+ can be unequivocally attributed to low-spin d⁶, d⁵, and d⁴ complexes. The excited state landscape of the Fe^II and Fe^IV complexes is characterized by short-lived ³MLCT and ³LMCT states, with lifetimes of 5.1 and 1.4 ps, respectively. In the Fe^II-compound, an energetically low-lying MC state leads to fast deactivation of the MLCT state. The distorted square-pyramidal state, where one carbene is dissociated, can not only relax into the ground state, but also into a singlet dissociated state. Its formation was investigated with time-dependent optical spectroscopy, while insights into its structure were gained by NMR spectroscopy.