Oxidation of sulfide, phosphine, and benzyl substrates tethered to N-donor pyridine ligands in carboxylate-bridged diiron(II) complexes.

Substituted pyridines were employed to prepare a series of terphenylcarboxylate-bridged diiron(II) compounds to mimic aspects of the chemistry at the active sites of bacterial multicomponent monooxygenases, including soluble methane monooxygenase (sMMO) and toluene monooxygenase (ToMO). Complexes of general formula [Fe2(O2CArTol)4L], L = 2, 3, or 4-pyridyldiphenylphosphine, 2-pyridylphenylsulfide, or 2-benzylpyridine and ArTol = 2,6-di(p-tolyl)benzoate, were synthesized and characterized by X-ray crystallography. Upon exposure of these compounds to dioxygen, ligand oxidation ensued and, in one case, proceeded catalytically.