A bench-stable fluorophosphine nickel(0) complex and its catalytic application

We herein present a bench-stable fluorophosphine-based nickel(0) complex [Ni(PFPh2)4] (1), which is highly stable in air and water. This complex does not only incorporate a nickel centre in the zero-oxidation state, but also includes fluorophosphine ligands. Since these ligands typically tend to disproportionation in solution, they represent a vastly underexplored ligand class. [Ni(PFPh2)4] can be obtained from a one-pot reaction of [Ni(MeCN)4](BF4)2 with Ph2P(=O)–PPh2, involving a unique in-situ reduction of Ni(II) to Ni(0) and the simultaneous fluorination by the BF4– anion. The application of [Ni(PFPh2)4] as highly stable Ni(0) pre-catalyst in combination with additional phosphine ligands, such as dppf (1,1'-bis(diphenylphosphino)ferrocene) in Suzuki-Miyaura coupling reactions uncovers its high catalytic activity, which is greatly superior to the conventional Ni(0) source [Ni(COD)2]. A remarkable catalytic activity is achieved through the combination of 1 and dppf after a light-induced activation of the complex.