;
• Sanford, Melanie S.

Abstract

Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni⁰, 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(sp³)-oxygen, carbon(sp³)-nitrogen, and carbon(sp³)-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.