Ligand-centered redox activity in cobalt(II) and nickel(II) bis(phenolate)-dipyrrin complexes.

One for all: a trianionic ligand containing the biologically relevant moieties phenolate and porphyrin was designed and synthesized. One-electron oxidation of the nickel and cobalt complexes of these ligands affords an unprecedented and highly stable hybrid porphyrinyl-phenoxyl radical bound to the metal center. Two-electron oxidation of these complexes leads to the M(2+) -(close-shell two-electron oxidized ligand) species.