Abstract
Detailed herein is the synthesis and characterization of [P,N]-ligated perfluoronickelacyclopentanes based on the bidentate ligand 2-(diphenylphosphino)phenyl-N-phenylaniline [P,NH]. A high-yielding substitution reaction between [P(O-o-tol)(3)](2)Ni(C4F8) and [P,NH] gives the phosphine-amine-coordinated metallacycle [P,NH]Ni(C4F8). Alternatively, [P,NH]Ni(C4F8) is formed upon treatment of Ni[P(O-o-tol)(3)](4) with one equiv. of [P,NH] followed by tetrafluoroethylene. This product reacts quantitatively with base to give an anionic phosphine-amido-ligated nickelacycle. Reactivity studies of the new [P,NH]- and [P,N-]-ligated perfluoronickelacycles are presented and compared and contrasted with our previously reported [P,S] systems. (C) 2018 Elsevier Ltd. All rights reserved.