Sulfur-Ligated [2Fe-2C] Clusters as Synthetic Model Systems for Nitrogenase.
Inorganic chemistry(2023)
摘要
Metal clusters featuring carbon and sulfur donors have coordination environments comparable to the active site of nitrogenase enzymes. Here, we report a series of di-iron clusters supported by the dianionic yldiide ligands, in which the Fe sites are bridged by two μ-C atoms and four pendant S donors.The [LFe] (L = {[PhP(S)]C}) cluster is isolable in two oxidation levels, all-ferrous Fe and mixed-valence FeFe. The mixed-valence cluster displays two peaks in the Mössbauer spectra, indicating slow electron transfer between the two sites. The addition of the Lewis base 4-dimethylaminopyridine to the Fe cluster results in coordination with only one of the two Fe sites, even in the presence of an excess base. Conversely, the cluster reacts with 8 equiv of isocyanide BuNC to give a monometallic complex featuring a new C-C bond between the ligand backbone and the isocyanide. The electronic structure descriptions of these complexes are further supported by X-ray absorption and resonant X-ray emission spectroscopies.
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关键词
nitrogenase,clusters,synthetic model systems,sulfur-ligated
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