title: Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes.
abstract: Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), 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-heteroatom coupling reactions.
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
authors.forename: Nicole M
authors.initials: NM
authors.lastname: Camasso
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA. mssanfor@umich.edu.
authors.forename: Melanie S
authors.initials: MS
authors.lastname: Sanford