O2 Activation by Non-Heme Thiolate-Based Dinuclear Fe Complexes
| Autor: | Marcello Gennari, Serhiy Demeshko, Lianke Wang, Christian Philouze, Franc Meyer, Sam P. de Visser, David Flot, Wesley R. Browne, Sandeep K. Padamati, Fabián G. Cantú Reinhard, Carole Duboc |
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| Přispěvatelé: | Univ. Grenoble Alpes, CNRS, DCM, 38000 Grenoble, France, Institutes of Physical Science and Information Technology, Anhui University, Manchester Institute of Biotechnology and Department of Chemical Engineering and Analytical Science, Stratingh Institute for Chemistry and Chemical Engineering, University of Groningen [Groningen], European Synchrotron Radiation Facility (ESRF), Institute of Inorganic Chemistry, Georg-August-University [Göttingen], Molecular Inorganic Chemistry |
| Rok vydání: | 2020 |
| Předmět: |
MECHANISM
Coordination sphere Dimer Protonation Crystal structure 010402 general chemistry 01 natural sciences Redox Inorganic Chemistry chemistry.chemical_compound [CHIM]Chemical Sciences CRYSTAL-STRUCTURE Reactivity (chemistry) Physical and Theoretical Chemistry ComputingMilieux_MISCELLANEOUS DIMER 010405 organic chemistry Chemistry Ligand IRON OXYGENATION Comproportionation REACTIVITY 0104 chemical sciences MODEL Crystallography CYSTEINE DIOXYGENASE LIGAND BOND |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2020, 59 (5), pp.3249-3259. ⟨10.1021/acs.inorgchem.9b03633⟩ Inorganic Chemistry, 59(5), 3249-3259. AMER CHEMICAL SOC |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | 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 O2 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, [FeII 2(LS)2] (LS2- = 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, [FeII 2(LS)(LSH)]+. When reaction with O2 occurs in the absence of protons or in the presence of 1 equiv of proton (i.e., from [FeII 2(LS)(LSH)]+), unsupported μ-oxo or μ-hydroxo FeIII dinuclear complexes ([FeIII 2(LS)2O] and [FeIII 2(LS)2(OH)]+, respectively) are generated. [FeIII 2(LS)2O], reported previously but isolated here for the first time from O2 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 FeIII dimers, suggesting that a dinuclear μ-peroxo FeIII 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. |
| Databáze: | OpenAIRE |
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