Wang, Lianke Gennari, Marcello Cantú Reinhard, Fabián G. Padamati, Sandeep K. Philouze, Christian Flot, David Demeshko, Serhiy Browne, Wesley R. Meyer, Franc de Visser, Sam P. Duboc, Carole O<sub>2</sub> Activation by Non-Heme Thiolate-Based Dinuclear Fe Complexes Iron centers featuring thiolates in their metal coordination sphere (as ligands or substrates) are well-known to activate dioxygen. Both heme and non-heme centers that contain iron-thiolate bonds are found in nature. Investigating the ability of iron–thiolate model complexes to activate O<sub>2</sub> is expected to improve the understanding of the key factors that direct reactivity to either iron or sulfur. We report here the structural and redox properties of a thiolate-based dinuclear Fe complex, [Fe<sup>II</sup><sub>2</sub>(LS)<sub>2</sub>] (LS<sup>2–</sup> = 2,2′-(2,2′-bipyridine-6,6′-iyl)­bis­(1,1-diphenylethanethiolate)), and its reactivity with dioxygen, in comparison with its previously reported protonated counterpart, [Fe<sup>II</sup><sub>2</sub>(LS)­(LSH)]<sup>+</sup>. When reaction with O<sub>2</sub> occurs in the absence of protons or in the presence of 1 equiv of proton (i.e., from [Fe<sup>II</sup><sub>2</sub>(LS)­(LSH)]<sup>+</sup>), unsupported μ-oxo or μ-hydroxo Fe<sup>III</sup> dinuclear complexes ([Fe<sup>III</sup><sub>2</sub>(LS)<sub>2</sub>O] and [Fe<sup>III</sup><sub>2</sub>(LS)<sub>2</sub>(OH)]<sup>+</sup>, respectively) are generated. [Fe<sup>III</sup><sub>2</sub>(LS)<sub>2</sub>O], reported previously but isolated here for the first time from O<sub>2</sub> activation, is characterized by single crystal X-ray diffraction and Mössbauer, resonance Raman, and NMR spectroscopies. The addition of protons leads to the release of water and the generation of a mixture of two Fe-based “oxygen-free” species. Density functional theory calculations provide insight into the formation of the μ-oxo or μ-hydroxo Fe<sup>III</sup> dimers, suggesting that a dinuclear μ-peroxo Fe<sup>III</sup> intermediate is key to reactivity, and the structure of which changes as a function of protonation state. Compared to previously reported Mn–thiolate analogues, the evolution of the peroxo intermediates to the final products is different and involves a comproportionation vs a dismutation process for the Mn and Fe derivate, respectively. O 2 Activation;Non-Heme Thiolate-Based Dinuclear Fe Complexes Iron centers;μ- oxo;μ- hydroxo Fe III dimers;NMR;OH;thiolate-based dinuclear Fe;metal coordination sphere;O 2 activation;Fe II 2;crystal X-ray diffraction;Fe III 2;O 2;dinuclear μ- peroxo Fe III;LS 2020-02-14
    https://acs.figshare.com/articles/journal_contribution/O_sub_2_sub_Activation_by_Non-Heme_Thiolate-Based_Dinuclear_Fe_Complexes/11855598
10.1021/acs.inorgchem.9b03633.s002