The [C4F8] ligand was shown to support well-defined terpyridyl nickel complexes in the +2 and +3 oxidation states. Notably, a cyclic voltammetry study of the nickel(iii) species indicates that an additional oxidation is accessible, providing a family of related fluoroalkyl nickel complexes spanning the +2 to +4 oxidation states.

The preparation of new dizinc reagents [(MeCN) 2 Zn((CF 2 ) n ) 2 Zn(MeCN) 2 ] (n = 3, 4, and 6) is reported. We show that the C4 reagent can readily transmetalate nickel to form a mononuclear perfluoronickelacycle. We also demonstrate that the reagents can be used to prepare novel fluoroorganics containing either perfluoroalkyl ring systems or perfluoroalkyl linked arenes under relatively mild conditions.

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.