Zirconium Complexes Supported by a Ferrocene-Based Ligand as Redox Switches for Hydroamination Reactions

The synthesis of (thiolfan*) Zr(NEt2)2 and (thiolfan*) Zr(NMe2)2 (thiolfan*= 1, 1'-bis (2,4-di-tert-butyl-6-thiophenoxy) ferrocene), and its selectivity towards catalyzing hydroamination reactions are reported. Switching the metal complex in situ between its oxidized and reduced states with redox reagents resulted in selectivity. We found that the reduced form of (thiolfan*)Zr(NEt2)2 can catalyze hydroamination reactions of primary aminoalkenes, whereas the oxidized form, [(thiolfan*)Zr(NEt2)2][BArF] can catalyze hydroamination reactions of secondary aminoalkenes