Achieving Nickel Catalyzed C–S Cross-Coupling under Mild Conditions Using Metal–Ligand Cooperativity

A simple and efficient approach of C–S cross-coupling of a wide variety of (hetero)­aryl thiols and (hetero)­aryl halides under mild conditions, mostly at room temperature, catalyzed by well-defined singlet diradical Ni­(II) catalysts bearing redox noninnocent ligands is reported. Taking advantage of ligand centered redox events, the high-energetic Ni(0)/Ni­(II) or Ni­(I)/Ni­(III) redox steps were avoided in the catalytic cycle. The cooperative participation of both nickel and the coordinated ligands during oxidative addition/reductive elimination steps allowed us to perform the catalytic reactions under mild conditions.