Copper(I) complexes with tri-o-tolylphosphine and heterocyclic thione ligands. Crystal structures of [(pyrimidine-2-thione)(tri-o-tolylphosphine)copper(I) chloride] and [(pyridine-2-thione)(tri-o-tolylphosphine)copper(I) iodide

Abstract

Copper(I) complexes of the general formula [Cu(totp)(L)X], where X = Cl, I; totp = tri-ortho-tolylphosphine; L = pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), 1,3-thiazolidine-2-thione (tzdtH), 1-methyl-1,3-imidazole -2-thione (meimtH), benz-l,3-imidazoline-2-thione (bzimtH2) and quinoline-2-thione (qntH) were prepared and characterized by their IR, UV-Vis and 1H NMR spectroscopic data. The behaviour of the complexes upon photolysis in chloroform solutions has been investigated. The structures of [Cu(totp)(pymtH)Cl] and [Cu(totp)(tzdtH)I] were determined by X-ray diffraction: [Cu(totp)(pymtH)Cl] crystallizes in the trigonal space group P3 with a = 22.433(4), b = 22.433(4), c = 9.526(3) Å, γ=120° and Z = 6; [Cu(tzdtH)(totp)I] crystallizes in the monoclinic space group P21/n with a = 17.111(2), b = 10.505(1), c = 14.823(1) Å, β = 108.30(1)°, Z = 4. In both complexes the coordination around Cu is approximately trigonal planar. Steric protection at the central metal by the three methyl groups neighbouring the donor phosphorus of the phosphine ligand is likely to explain the preferential formation of three-coordinate complexes.