Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes

This paper describes the one-electron interconversions of isolable NiIII and NiIV complexes through their reactions with carbon-centered radicals (R•). First, model NiIII complexes are shown to react with alkyl and aryl radicals to afford NiIV products. Preliminary mechanistic studies implicate a pathway involving direct addition of a carbon-centered radical to the NiIII center. This is directly analogous to the known reactivity of NiII complexes with R•, a step that is commonly implicated in catalysis. Second, a NiIV–CH3 complex is shown to react with aryl and alkyl radicals to afford C–C bonds via a proposed SH2-type mechanism. This pathway is leveraged to enable challenging H3C–CF3 bond formation under mild conditions. Overall, these investigations suggest that NiII/III/IV sequences may be viable redox pathways in high-oxidation-state nickel catalysis.