High-valent corrole metal complexes.
This commentary concentrates on corrole complexes with the three metal ions that are most relevant to oxidation catalysis: chromium, manganese, and iron. Particular emphasis is devoted to the only recently introduced meso-triarylcorroles and a comparison with the traditionally investigated beta-pyrrole-substituted corroles. Based on a combination of spectroscopic methods, electrochemistry, and X-ray crystallography, it is concluded that in most high-valent metallocorroles the corrole is not oxidized. Both experimental (for (oxo)chromium(V) corrole) and computational (for (oxo)manganese(V) corrole) evidence indicate that the stabilization of high-valent metal ions by corroles originates from a combination of short metal-nitrogen bonds and large metal out-of-plane displacements in the corrole, which lead to quite unexpected interactions of the oxo-metal pi* orbitals with the in-plane orbitals of the corrole.
Gross
Z
Z
Department of Chemistry and Institute of Catalysis Science and Technology, Technion, Haifa, Israel. chr10ozg@tx.technion.ac.il
D045728:Corrinoids; D008958:Models, Molecular; D011166:Porphyrins / Q000737:chemistry*
D045728:Corrinoids; D011166:Porphyrins; C431863:corrole