Oxidative C-C bond formation reactivity of organometallic Ni(II), Ni(III), and Ni(IV) complexes

The use of the tridentate ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (Me₃tacn) and the cyclic alkyl/aryl C-donor ligand-CH₂CMe₂-o-C₆H₄-(cycloneophyl) allows for the synthesis of isolable organometallic Ni^II, Ni^III, and Ni^IV complexes. Surprisingly, the fivecoordinate Ni^III complex is stable both in solution and the solid state, and exhibits limited C-C bond formation reactivity. Oxidation by one electron of this Ni^III species generates a six-coordinate Ni^IV complex, with an acetonitrile molecule bound to Ni. Interestingly, illumination of the Ni^IV complex with blue LEDs results in rapid formation of the cyclic C-C product at room temperature. This reactivity has important implications for the recently developed dual Ni/photoredox catalytic systems proposed to involve high-valent organometallic Ni intermediates. Additional reactivity studies show the corresponding Ni^II species undergoes oxidative addition with alkyl halides, as well as rapid oxidation by O₂, to generate detectable Ni^III and/or Ni^IV intermediates and followed by C-C bond formation.