Dioxygen Reactivity of Biomimetic Fe(II) Complexes with Noninnocent Catecholate, o-Aminophenolate, and o-Phenylenediamine Ligands

This study describes the O2 reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine ((Ph2)TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate ((tBu)CatH(-)), 4,6-di-tert-butyl-2-aminophenolate ((tBu2)APH(-)), or 4-tert-butyl-1,2-phenylenediamine ((tBu)PDA). The preparation and X-ray structural characterization of [Fe(2+)((Ph2)TIP)((tBu)CatH)]OTf, [3]OTf and [Fe(2+)((Ph2)TIP)((tBu)PDA)](OTf)2, [4](OTf)2 are described here, whereas [Fe(2+)((Ph2)TIP)((tBu2)APH)]OTf, [2]OTf was reported in our previous paper [Bittner et al., Chem.-Eur. J. 2013, 19, 9686-9698]. These complexes mimic the substrate-bound active sites of nonheme iron dioxygenases, which catalyze the oxidative ring-cleavage of aromatic substrates like catechols and aminophenols. Each complex is oxidized in the presence of O2, and the geometric and electronic structures of the resulting complexes were examined with spectroscopic (absorption, EPR, Mössbauer, resonance Raman) and density functional theory (DFT) methods. Complex [3]OTf reacts rapidly with O2 to yield the ferric-catecholate species [Fe(3+)((Ph2)TIP)((tBu)Cat)](+) (3(ox)), which undergoes further oxidation to generate an extradiol cleavage product. In contrast, complex [4](2+) experiences a two-electron (2e(-)), ligand-based oxidation to give [Fe(2+)((Ph2)TIP)((tBu)DIBQ)](2+) (4(ox)), where DIBQ is o-diiminobenzoquinone. The reaction of [2](+) with O2 is also a 2e(-) process, yet in this case both the Fe center and (tBu2)AP ligand are oxidized; the resulting complex (2(ox)) is best described as [Fe(3+)((Ph2)TIP)((tBu2)ISQ)](+), where ISQ is o-iminobenzosemiquinone. Thus, the oxidized complexes display a remarkable continuum of electronic structures ranging from [Fe(3+)(L(2-))](+) (3(ox)) to [Fe(3+)(L(•-))](2+) (2(ox)) to [Fe(2+)(L(0))](2+) (4(ox)). Notably, the O2 reaction rates vary by a factor of 10(5) across the series, following the order [3](+) > [2](+) > [4](2+), even though the complexes have similar structures and Fe(3+/2+) redox potentials. To account for the kinetic data, we examined the relative abilities of the title complexes to bind O2 and participate in H-atom transfer reactions. We conclude that the trend in O2 reactivity can be rationalized by accounting for the role of proton transfer(s) in the overall reaction.