Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes

Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni-O, Ni-I, Ni-II, and/or Ni-III oxidation states. In contrast, Ni-IV intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni-IV complexes, accessed by the reaction of Ni-II precursors with the widely used oxidant S-(trifluoromethyl) dibenzothiophenium triflate. These Ni-IV complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-hetero-atom coupling reactions.