Recent developments in nickel-catalyzed C-C and C-heteroatom coupling reactions have implicated the intermediacy of NiIV complexes. However, these putative NiIV intermediates have not been directly detected, and only inferred through radical trapping experiments. This presentation describes the design and implementation of a model system that allows for the isolation and reactivity studies of NiIV(aryl)(CF3) compounds. Aryl diazonium and diaryliodonium reagents are found to effect the 2e- oxidation of NiII(Tp)(CF3)2 compounds. The resulting stable NiIV(Tp)(CF3)2(Ar) complexes mediate high yielding Ar-CF3 bond-forming reductive elimination under mild thermolytic conditions. These experiments provide strong evidence for the feasibility of NiII/IV-catalyzed reactions using strong aryl electrophiles.

Synthesis and reactivity of high-valent organometallic nickel complexes bearing trifluoromethyl ligands

251st National Meeting (2016)

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