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Updated: Aug 22, 2025

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Nickel(IV) Intermediates in Aminoquinoline-Directed C(sp2)-C(sp3) Coupling
Michael W Milbauer1, Jeff W Kampf1, Melanie S Sanford1
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
Abstract:
We use a ligand design strategy to isolate a cyclometalated nickel(IV) complex that is directly analogous to a key intermediate proposed in aminoquinoline-directed C-H functionalization catalysis. This nickel(IV) complex is formed by oxidative addition of a diaryliodonium reagent to an anionic nickel(II)-picolinate precursor. The nickel(IV) σ-aryl complex is stable at room temperature but undergoes C(sp2)-C(sp3) bond-forming reductive elimination under mild conditions (70 °C, 120 min). Overall, this study demonstrates the accessibility of long-sought-after nickel(IV) intermediates in C-H functionalization catalysis. Furthermore, it demonstrates that LX-type (bidentate, mono-anionic) ligands such as picolinate dramatically stabilize these nickel(IV) species.
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