X‑ray Absorption and Emission Spectroscopies of X‑Bridged Diiron Phthalocyanine Complexes (FePc)2X (X = C, N, O) Combined with DFT Study of (FePc)2X and Their High-Valent Diiron Oxo Complexes

μ-Nitrido diiron phthalocyanine [PcFe+3.5NFe+3.5Pc]0 is an efficient catalyst, able to catalyze the oxidation of methane under near-ambient conditions. In this work, we compared the properties of structurally similar μ-carbido (1), μ-nitrido (2), and μ-oxo (3) dimers of iron phthalocyanine. The goal was to discern the structural and electronic differences between these complexes and to propose a rationale for the exceptional activity of 2. Extended X-ray fine-structure spectroscopy, high-resolution X-ray emission spectroscopy, and resonant inelastic X-ray scattering were applied to study the geometry and electronic structure of iron species in the series 13. The data provided by core hole spectroscopies were compared to the results of DFT calculations and found to coherently describe the structural and electronic properties of 13 as having equivalent iron centers with formal iron oxidation degrees of 3, 3.5, and 4 for the μ-oxo, μ-nitrido, and μ-carbido dimers, respectively. However, the bond length to the bringing atom changed in an unexpected sequence Fe–O > Fe–N < Fe–C, indicating redox non-innocence of the brigding μ-carbido ligand in 1. According to the X-ray emission spectroscopy, the μ-nitrido dimer 2 is a low-spin compound, with the highest covalency in the series 13. The DFT-calculated geometry and electronic structures as well as core hole spectra of hypothetical high-valent oxo complexes of 13 were compared, in order to explain the particular catalytic activity of 2 and to estimate the prospects of spectroscopic observation of such species. It appears that the terminal FeO bond is the longest in the oxo complex of 2, due to the strong trans-effect of the nitrido ligand. The corresponding LUMO of the μ-nitrido diiron oxo complex has the lowest energy among the three oxo complexes. Therefore, the oxo complex of 2 is expected to have the highest oxidative power.