Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase

The one‐electron oxidations of a Fe₂ complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe₂ species, mixed‐valent Fe₄, and Fe₈ complexes. The unpaired spin in the Fe₂ radical species delocalizes over the Fe₂ and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe₂ to the Fe₄ retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe₈, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe₈ is converted to Fe₄. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes.     

Triphenylphosphine‐Mediated Deoxygenative Reduction of CF3SO2Na and Its Application for Trifluoromethylthiolation of Aryl Iodides

We report herein a practical method for taming Langlois’ reagent CF₃SO₂Na to generate CuSCF₃ by a triphenylphospine‐mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF₃S skeleton of Langlois’ reagent as a CF₃S feedstock under mild conditions. The CuSCF₃ intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air‐stable [LCu(SCF₃)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF₃ intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency.