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

摘要

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, combined with a ligand field analysis of the Fe K pre-edge to a low-spin ferric corrole, and compare it to a low-spin ferric porphyrin. The experimental results combined with DFT calculations show that the contracted corrole is both a stronger σ donor and a very anisotropic π donor. These differences decrease the bonding interactions with axial ligands and contribute to the increased axial ligand lability and reactivity of ferric corroles relative to ferric porphyrins.