SYNTHESIS AND PHOTOLYSIS OF MIXED COPPER(I) COMPLEXES WITH THIONES AND TRI-PARA-TOLYLPHOSPHINE OR TRIPHENYLPHOSPHINE - X-RAY CRYSTAL-STRUCTURE OF BIS[COPPER(I)(1,3-THIAZOLIDINE-2-THIONE) (TRI-PARA-TOLYLPHOSPHINE)CHLORIDE]

Reaction of [Cu(PR3)Cl]4 [where PR3 = tri-p-tolylphosphine (tptp), or triphenylphosphine(tpp)] with several heterocyclic thiones (L) yields binuclear complexes of the general formula [Cu(PR3)(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 Cu2S2 core remained intact. The crystal structure of [Cu(tptp)(tzdtH)Cl]2 has been established by single-crystal X-ray diffraction methods. In the Cu2S2 core the Cu-S bond lengths are 2.386(1) and 2.470(1) angstrom. The Cu-P and Cu-Cl distances are 2.222(1) and 2.283(1) angstrom, respectively.