SYNTHESES AND CRYSTAL-STRUCTURES OF NICKEL(II) COMPLEXES WITH THIOLATE OR/AND PHOSPHINE-LIGANDS

The reactions of Ni2+, edt(2-) and PR(3) (R = Ph or Et) in MeOH gave the complexes [Ni(tpdt)(PPh(3))] 1, [Ni-2(edt)(2)(PPh(3))(2)] 2, [Ni-2(edt)(2)(PEt(3))(2)] 3 and [Ni-2(tpdt)(2)] 4 (edt = ethane-l,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) Angstrom, 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) Angstrom, 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.