Synthesis and photolysis of mixed copper(I) complexes with thiones and tri- p-tolylphosphine or triphenylphosphine; X-ray crystal structure of bis[copper(I)(1,3-thiazolidine-2-thione) (tri- p-tolylphosphine)chloride

Abstract

Reaction of [Cu(PR 3)Cl] 4 [where PR 3 = tri- p-tolylphosphine (tptp), or triphenylphosphine (tpp)] with several heterocyclic thiones (L) yields binuclear complexes of the general formula [Cu(PR 3)(L)Cl] 2 [L = 1,3-thiazolidine-2-thione (tzdtH), benz-1,3- thiazoline-2-thione (bztztH), dithiouracil (dtu), purine-6-thione (pur6SH) and thiourea (tu)]. Irradition of the complexes, in chloroform, methanol and acetonitrile solutions, caused phosphine evolution while the Cu 2S 2 core remained intact. The crystal structure of [Cu(tptp)(tzdtH)Cl] 2 has been established by single-crystal X-ray diffraction methods. In the Cu 2S 2 core the CuS bond lengths are 2.386(1) and 2.470(1) Å. The CuP and CuCl distances are 2.222(1) and 2.283(1) Å, respectively.