A Modular, Air-Stable Nickel Precatalyst

The synthesis and catalytic activity of [(TMEDA)­Ni­(o-tolyl)­Cl], an air-stable, crystalline solid, is described. This complex is an effective precatalyst in a variety of nickel-catalyzed transformations. The lability of TMEDA allows a wide variety of ligands to be used, including mono- and bidentate phosphines, diimines, and N-heterocyclic carbenes. Preliminary mechanistic studies are also reported, which suggest that [(TMEDA)­Ni­(o-tolyl)­Cl] can activate by either a Ni–B or Ni–Ni transmetalation event, depending on the reaction conditions.