Syntheses and crystal structures of nickel(II) complexes with thiolate or/and phosphine ligands

Abstract

The reactions of Ni²⁺, edt^2– and PR₃(R = Ph or Et) in MeOH gave the complexes [Ni(tpdt)(PPh₃)]1, [Ni₂(edt)₂(PPh₃)₂]2, [Ni₂(edt)₂(Pet₃)₂]3 and [Ni₂(tpdt)₂]4(edt = ethane-1,2-dithiolate, tpdt = 3-thiapentane-1,5-dithiolate). Complex 3 is orthorhombic and crystallizes in space group Pbca with a= 14.086(4), b= 25.569(11), c= 13.768(4)Å, Z= 8, R= 0.060. Complex 4 also crystallizes in the orthorhombic space group Pbca with a= 10.935(8), b= 28.826(15), c= 9.437(4)Å, Z= 8, R= 0.047. All the nickel atoms are four-co-ordinated with distorted square-planar geometies of phosphorus and/or sulfur atoms. In the reaction system condensation of edt^2– occurs through a C–S bond disruption to form tpdt^2–, which co-ordinates to the nickel atoms to give complexes 1 and 4.