Oxidation of Sulfide, Phosphine, and Benzyl Substrates Tethered to N-Donor Pyridine Ligands in Carboxylate-Bridged Diiron(II) Complexes

2004-03-24T00:00:00Z (GMT) by Emily C. Carson Stephen J. Lippard
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 [Fe<sub>2</sub>(O<sub>2</sub>CAr<sup>Tol</sup>)<sub>4</sub>L], L = 2, 3, or 4-pyridyldiphenylphosphine, 2-pyridylphenylsulfide, or 2-benzylpyridine and Ar<sup>Tol</sup> = 2,6-di(<i>p</i>-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.