AI Article Synopsis
- The study explores di-iron clusters that mimic the nitrogenase enzyme's active site, utilizing yldiide ligands with carbon and sulfur donors.
- The [LFe] cluster can exist in two oxidation states, showcasing unique electron transfer behavior observed in Mössbauer spectra.
- Reactions with Lewis bases and isocyanides reveal further insights into the cluster's coordination chemistry and electronic structure through advanced spectroscopic techniques.
Article Abstract
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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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9930126 | PMC |
| http://dx.doi.org/10.1021/acs.inorgchem.2c03693 | DOI Listing |
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