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

• DOI: 10.1126/science.aaa4526
• Publication Date: 2015-02-06T05:02:08Z
• Authors: Nicole M. Camasso; Melanie S. Sanford
• Keywords: Heteroatom; Trifluoromethanesulfonate; Reactivity; Organometallic Chemistry; Coupling reaction; Carbon fibers; Reactive intermediate

Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via intermediates in Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) are rarely accessible. We report herein design, synthesis, characterization a series organometallic complexes, accessed by reaction Ni(II) precursors with widely oxidant S-(trifluoromethyl)dibenzothiophenium triflate. complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, carbon(sp(3))-sulfur coupling exogenous nucleophiles. The observed reactivity has potential direct applications development nickel-catalyzed carbon-heteroatom reactions.