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 (Metacn) and the cyclic alkyl/aryl C-donor ligand -CHCMe-o-CH- (cycloneophyl) allows for the synthesis of isolable organometallic Ni, Ni, and Ni complexes. Surprisingly, the five-coordinate Ni 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 species generates a six-coordinate Ni complex, with an acetonitrile molecule bound to Ni. Interestingly, illumination of the Ni 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 species undergoes oxidative addition with alkyl halides, as well as rapid oxidation by O, to generate detectable Ni and/or Ni intermediates and followed by C-C bond formation.