Phosphorus–fluorine compounds. Part XIV. Direct syntheses of tetrakis(fluorophosphine) complexes of zerovalent nickel

Abstract

Metallic nickel (formed by decarboxylation of nickel oxalate) reacts directly with several fluorophosphines, R_nPF_{3 –n}, at 60° to produce the corresponding zerovalent nickel complex NiL₄[L = PF₃, CF₃PF₂, (CF₃)₂PF, CCl₃PF₂, Me₂NPF₂, and C₅H₁₀NPF₂]. The complex Ni[ClCH₂PF₂]₄ which could not be formed in this way was made by the reaction of the ligand with nickelocene; its i.r. spectrum and fluorine, phosphorus, and proton n.m.r. spectra are presented. Analysis of the ¹⁹F n.m.r. spectrum gives an accurate value for |¹J_PF+ 3³J_PF′| and approximate values for |¹J_PF|, |³J_PF|, |²J_PP|, and |⁴J_FF′|. ³¹P Chemical shift data for all the complexes are presented and discussed.