Synthesis of a Nitrogenase P N ‐Cluster Model with [Fe 8 S 7 (μ‐S thiolate ) 2 ] Core from the All‐Ferric [Fe 4 S 4 (S thiolate ) 4 ] Cubane Synthon
| Autor: | Tsuyoshi Matsumoto, Ayaka Nagasaki, Golam Moula, Kazuyuki Tatsumi, Matthias E. Miehlich, Karsten Meyer, Roger E. Cramer |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Sulfide Trimethylsilyl 010405 organic chemistry Synthon Nitrogenase General Medicine General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry.chemical_compound Crystallography chemistry Cubane Mössbauer spectroscopy medicine Cluster (physics) Ferric medicine.drug |
| Zdroj: | Angewandte Chemie International Edition. 60:15792-15797 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.202102369 |
| Popis: | Constructing synthetic models of the nitrogenase PN -cluster has been a long-standing synthetic challenge. Here, we report an optimal nitrogenase PN -cluster model [{(TbtS)(OEt2 )Fe4 S3 }2 (μ-STbt)2 (μ6 -S)] (2) [Tbt=2,4,6-tris{bis(trimethylsilyl)methyl}phenyl] that is the closest synthetic mimic constructed to date. Of note is that two thiolate ligands and one hexacoordinated sulfide are connecting the two Fe4 S3 incomplete cubanes similar to the native PN -cluster, which has never been achieved. Cluster 2 has been characterized by X-ray crystallography and relevant physico-chemical methods. The variable temperature magnetic moments of 2 indicate a singlet ground state (S=0). The Mossbauer spectrum of 2 exhibits two doublets with an intensity ratio of 3:1, which suggests the presence of two types of iron sites. The synthetic pathway of the cluster 2 could indicate the native PN -cluster maturation process as it has been achieved from the Fe4 S4 cubane Fe4 S4 (STbt)4 (1). |
| Databáze: | OpenAIRE |
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