Effect of Oxidation and Protonation States on [2Fe–2S] Cluster Nitrosylation Giving {Fe(NO)2}9 Dinitrosyl Iron Complexes (DNICs)
| Autor: | Marie Bergner, Christine E. Schiewer, Juliusz A. Wolny, Franc Meyer, Christina S. Müller, Volker Schünemann, Sebastian Dechert |
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| Rok vydání: | 2018 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 58:769-784 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.8b02927 |
| Popis: | The nitrosylation of biological Fe/S clusters to give protein-bound dinitrosyl iron complexes (DNICs) is physiologically important. Biomimetic studies on the reaction of synthetic [2Fe–2S] clusters with NO have so far been limited to diferric model complexes. This work now compares the nitrosylation of [2Fe–2S] clusters with SN- or NN-chelating benzimidazolate/thiophenolate or bis(benzimidazolate) capping ligands in their diferric (12– and 22–) and mixed-valent (FeIIFeIII, 13–, and 23–) forms. Furthermore, the effect of protonation of the imidazole part of the SN ligand has been probed on both the nitrosylation reaction and properties of the resulting DNIC. The reaction of 12– and 22– with 4 equiv NO yields the new anionic {Fe(NO)2}9 DNICs 3– and 4–, respectively, which have been comprehensively characterized, including X-ray crystallography of their PPN+ salts. Nitrosylation of mixed-valent [2Fe–2S] clusters 13– and 23– first leads to slow oxidation to the corresponding diferric congeners, followed by co... |
| Databáze: | OpenAIRE |
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