A Bench‐Stable Fluorophosphine Nickel(0) Complex and Its Catalytic Application

We herein present a fluorophosphine-based nickel(0) complex [Ni(PFPh₂)₄] (1), which is highly stable in air and water. [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 a simultaneous fluorination by the BF₄ ^- anion. This complex does not only incorporate a nickel center in the zero-oxidation state, resulting from a Ni(II) precursor, but also includes fluorophosphine ligands, which typically disproportionate immediately in solution. 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 various coupling reactions uncovers its high catalytic activity and versatility, which is superior to [Ni(COD)₂] (COD═cycloocta-1,5-diene) as conventional Ni(0) source.