Dioxygen-Initiated Oxidation of Heteroatomic Substrates Incorporated into Ancillary Pyridine Ligands of Carboxylate-Rich Diiron(II) Complexes

Progress toward the development of functional models of the carboxylate-bridged diiron active site in soluble methane
monooxygenase is described in which potential substrates are introduced as substituents on bound pyridine ligands.
Pyridine ligands incorporating a thiol, sulfide, sulfoxide, or phosphine moiety were allowed to react with the
preassembled diiron(II) complex [Fe2(μ-O2CArR)2(O2CArR)2(THF)2], where -O2CArR is a sterically hindered 2,6-di(p-tolyl)- or 2,6-di(p-fluorophenyl)benzoate (R = Tol or 4-FPh). The resulting diiron(II) complexes were characterized
crystallographically. Triply and doubly bridged compounds [Fe2(μ-O2CArTol)3(O2CArTol)(2-MeSpy)] (4) and
[Fe2(μ-O2CArTol)2(O2CArTol)2(2-MeS(O)py)2] (5) resulted when 2-methylthiopyridine (2-MeSpy) and 2-pyridylmethylsulfoxide (2-MeS(O)py), respectively, were employed. Another triply bridged diiron(II) complex, [Fe2(μ-O2CAr4-FPh)3-(O2CAr4-FPh)(2-Ph2Ppy)] (3), was obtained containing 2-diphenylphosphinopyridine (2-Ph2Ppy). The use of
2-mercaptopyridine (2-HSpy) produced the mononuclear complex [Fe(O2CArTol)2(2-HSpy)2] (6a). Together with that
of previously reported [Fe2(μ-O2CArTol)3(O2CArTol)(2-PhSpy)] (2) and [Fe2(μ-O2CArTol)3(O2CArTol)(2-Ph2Ppy)] (1), the
dioxygen reactivity of these iron(II) complexes was investigated. A dioxygen-dependent intermediate (6b) formed
upon exposure of 6a to O2, the electronic structure of which was probed by various spectroscopic methods. Exposure
of 4 and 5 to dioxygen revealed both sulfide and sulfoxide oxidation. Oxidation of 3 in CH2Cl2 yields [Fe2(μ-OH)2(μ-O2CAr4-FPh)(O2CAr4-FPh)3(OH2)(2-Ph2P(O)py)] (8), which contains the biologically relevant {Fe2(μ-OH)2(μ-O2CR)}3+ core. This reaction is sensitive to the choice of carboxylate ligands, however, since the p-tolyl analogue
1 yielded a hexanuclear species, 7, upon oxidation.