Fe L- and K-edge XAS of Low-Spin Ferric Corrole: Bonding and Reactivity Relative to Low-Spin Ferric Porphyrin

Corrole is a tetrapyrrolic macrocycle that has one carbon atom less than a porphyrin. The ring contraction reduces the symmetry from D4h to C2v, changes the electronic structure of the heterocycle, and leads to a smaller central cavity with three protons rather than the two of a porphyrin. The differences between ferric corroles and porphyrins lead to a number of differences in reactivity including increased axial ligand lability and a tendency to form 5-coordinate complexes. The electronic structure origin of these differences has been difficult to study experimentally as the dominant porphyrin/corrole π → π* transitions obscure the electronic transitions of the metal. Recently, we have developed a methodology that allows for the interpretation of the multiplet structure of Fe L-edges in terms of differential orbital covalency (i.e., the differences in mixing of the metal d orbitals with the ligand valence orbitals) using a valence bond configuration interaction model. Herein, we apply this methodology, ...