Low-coordinate bis-phosphine and monophosphine Ni(0) complexes: synthesis and reactivity in C-S cross-coupling

Preformed Ni(0) complexes are rarely used as precatalysts in cross-coupling reactions, although they can incorporate catalytically active nickel directly into the reaction. In this work, we focus on the preparation and the catalytic application of low-coordinate Ni(0) complexes supported by bulky monophosphine ligands in C-S cross-coupling reactions. We have prepared two families of Ni(0) complexes, bis-phosphine aducts of the type [Ni(PR₂Ar')₂] (Ar' = m-terphenyl group) and monophosphine derivatives of the type [Ni(PR₂Ar')(DVDS)] (DVDS = divinyltetramethyldisiloxane). DFT calculations were used to account for the atypical bent structures displayed by the bis-phosphine Ni(0) complexes. Monophosphine-Ni(0) complexes display catalytic activity superior to bis-phosphine Ni(0) adducts, which suggests that the former facilitate the generation of highly reactive monoligated PNi(0) species. Furthermore, the reactivity of monophosphine-Ni(0) precatalysts outperform that observed with Ni(II) precatalysts with the same phosphine ligands, supporting a more facile activation step to the same catalytic species. This enhanced reactivity allows for the use of lower catalyst loadings (1-5 mol%) and for carrying out the challenging coupling between aryl chlorides and alkylthiols.