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

Abstract We herein present a fluorophosphine‐based nickel(0) complex [Ni(PFPh 2 ) 4 ] ( 1 ), which is highly stable in air and water. [Ni(PFPh 2 ) 4 ] can be obtained from a one‐pot reaction of [Ni(MeCN) 4 ](BF 4 ) 2 with Ph 2 P(═O)–PPh 2 , involving a unique in situ reduction of Ni(II) to Ni(0) and a simultaneous fluorination by the BF 4 − 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(PFPh 2 ) 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.