Mononuclear iron complexes relevant to nonheme iron oxygenases. Synthesis, characterizations and reactivity of Fe-Oxo and Fe-Peroxo intermediates.

The new ligand L(6)(2)4E (N,N,N',N'-tetrakis(5-ethyl-2-pyridylmethyl)ethane-1,2-diamine) was designed as a more robust analog of TPEN (N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine) for which the ability at stabilizing high valent Fe-Oxo and Fe-(hydro)peroxo has been reported. With respect to the latter, the pyridyl beta-substituents in L(6)(2)4E do not modify the Fe coordination chemistry. From the Fe(II) precursor, [FeO](2+) and Fe(III)-(hydro)peroxo intermediates are prepared using the same synthetic methods as those reported for the TPEN analogs. The spectroscopic characteristics of all L(6)(2)4E-Fe complexes are very similar to their TPEN analog. However, [(L(6)(2)4E)FeO](2+) has a greater lifetime than that of [(TPEN)FeO](2+). This can be explained by a restricted bimolecular autodegradation due to the bulkiness provided by the ethyl substituents. Regarding small organic molecule oxidation, [(L(6)(2)4E)FeO](2+) and [(L(6)(2)4E)FeOOH](2+) exhibit behaviours that seem to be general for the complexes built with ligands of the TPEN family: [FeO](2+) appears to be efficient to epoxidize olefins, whereas [FeOOH](2+) hydroxylates the aromatic ring of anisole with efficacy.