Electronic, Magnetic, and Redox Properties and O₂ Reactivity of Iron(II) and Nickel(II) <i>o</i>‑Semiquinonate Complexes of a Tris(thioether) Ligand: Uncovering the Intradiol Cleaving Reactivity of an Iron(II) <i>o</i>‑Semiquinonate Complex

The iron­(II) semiquinonate character within the iron­(III) catecholate species has been proposed by numerous studies to account for the O₂ reactivity of intradiol catechol dioxygenases, but a well-characterized iron­(II) semiquinonate species that exhibits intradiol cleaving reactivity has not yet been reported. In this study, a detailed electronic structure description of the first iron­(II) <i>o</i>-semiquinonate complex, [PhTt^tBu]­Fe­(phenSQ) [PhTt^tBu = phenyltris­(<i>tert</i>-butylthiomethyl)­borate; phenSQ = 9,10-phenanthrenesemiquinonate; Wang et al. <i>Chem. Commun.</i> <b>2014</b>, <i>50</i>, 5871–5873], was generated through a combination of electronic and Mössbauer spectroscopies, SQUID magnetometry, and density functional theory (DFT) calculations. [PhTt^tBu]­Fe­(phenSQ) reacts with O₂ to generate an intradiol cleavage product, diphenic anhydride, in 16% yield. To assess the dependence of the intradiol reactivity on the identity of the metal ion, the nickel analogue, [PhTt^tBu]­Ni­(phenSQ), and its derivative, [PhTt^tBu]­Ni­(3,5-DBSQ) (3,5-DBSQ = 3,5-di-<i>tert</i>-butyl-1,2-semiquinonate), were prepared and characterized by X-ray crystallography, mass spectrometry, ¹H NMR and electronic spectroscopies, and SQUID magnetometry. DFT calculations, evaluated on the basis of the experimental data, support the electronic structure descriptions of [PhTt^tBu]­Ni­(phenSQ) and [PhTt^tBu]­Ni­(3,5-DBSQ) as high-spin nickel­(II) complexes with antiferromagnetically coupled semiquinonate ligands. Unlike its iron counterpart, [PhTt^tBu]­Ni­(phenSQ) decomposes slowly in an O₂ atmosphere to generate 14% phenanthrenequinone with a negligible amount of diphenic anhydride. [PhTt^tBu]­Ni­(3,5-DBSQ) does not react with O₂. This dramatic effect of the metal-ion identity supports the hypothesis that a metal­(III) alkylperoxo species serves as an intermediate in the intradiol cleaving reactions. The redox properties of all three complexes were probed using cyclic voltammetry and differential pulse voltammetry, which indicate an inner-sphere electron-transfer mechanism for the formation of phenanthrenequinone. The lack of O₂ reactivity of [PhTt^tBu]­Ni­(3,5-DBSQ) can be rationalized by the high redox potential of the metal-ligated 3,5-DBSQ/3,5-DBQ couple