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For relatively electron-rich corrole ligands, the halfwave potentials for oxidation of Cu(III), Sn(IV)Ph, Fe(IV)Ph, and Fe(IV)-O-Fe(IV) complexes are significantly lower than those of Sn(IV)Cl, Fe(IV)Cl, Mn(IV)Cl, and Cr(V)(O) complexes, suggesting that the corrole ligand is relatively electron-rich or 'innocent' in the former group of complexes and that it is relatively electron-deficient or 'noninnocent'...
Abstract. Using density functional theory, we have carried out a quantum chemical survey of high-valent transition metal porphyrins and related compounds. Discussed herein are recent developments on metalloporphyrin -cation radicals, high-valent manganese and iron porphyrins and heme protein intermediates, nickel(III) porphyrinoids, coenzyme F430, and high-valent transition metal corroles. In particular,...
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