6533b838fe1ef96bd12a4330

RESEARCH PRODUCT

Electrochemistry of Mono- and Bis-CN Ligated Cobalt Corroles

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description

International audience; The electrochemical properties of numerous transition metal corroles have been examined under a variety of<br&gtsolution condition with special emphasis being placed on the innocent or non-innocent nature of the corrole<br&gtmacrocycle. This property, as well as the half-wave potentials and sites of electron transfers, are known to be<br&gtstrongly influenced by the type of central metal ion and degree of axial coordination, namely 4, 5 or 6-coordinate.<br&gtThe redox potentials of metallocorroles are also dependent upon the solvent and inductive, resonance or steric<br&gteffects dictated by peripheral substituents at the meso or β-pyrrole positions of the corrole ligand. Our laboratories<br&gthave previously investigated five- and six- coordinate cobalt corroles with P, N or O donor ligands and in this work we describe the electrochemical and spectroscopic properties of several newly synthesized cobalt corroles which are axially ligated by one or two cyanide ions. Examples of the corroles to be described are shown in Chart 1 and represented as [(R)3CorCo(CN)]- and [(R)3CorCo(CN)2]2- where (R)3Cor is the corrole macrocycle and R is one of several meso-phenyl rings containing electron-withdrawing or electron-donating substituents. This work follows from an initial report where several bis-ligated complexes were in-situ generated and electrochemically characterized.