SYNTHESIS AND PHOTOLYSIS OF A NEW SERIES OF CU(I) COMPLEXES WITH TRI-META-TOLYLPHOSPHINE AND HETEROCYCLIC THIONES - THE CRYSTAL-STRUCTURE OF BIS[MU-IODO(PYRIDINE-2-THIONE)(TRI-META-TOLYLPHOSPHINE)COPPER(I)]

Reactions of [Cu(tmtp)I]4 (tmtp = tri-m-tolylphosphine) with heterocyclic thiones (L) (L = pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), 1,3-thiazolidine-2-thione (tzdtH), 1-methyl-1,3-imidazoline-2-thione (meimtH), benz-1,3-imidazoline-2-thione (bzimtH-2) and quinoline-2-thione (qntH)) yield binuclear complexes of the general formula [Cu(tmtp)(L)I]2. The complexes have been characterized by elemental analyses and their IR, UV-Vis and H-1 NMR spectroscopic data. The photolysis of these complexes in dichloromethane solutions has been investigated. The crystal structure of [Cu(tmtp)-(py2SH)I]2 has been determined by single-crystal X-ray diffraction methods. The orange crystals are triclinic, space group P1BAR with a = 9.9881(6), b = 10.8255(5), c = 13.5355(8) angstrom, alpha = 77.268(2), beta = 94.409(2), gamma = 68.102(2)-degrees, D(calc) = 1.543 Mg m-3, V = 1303.94(2) angstrom 3 and Z = 1. The molecule contains a planar Cu2I2 moiety with Cu-I bond lengths of 2.690(1) and 2.695(1) angstrom. The Cu-P and Cu-S distances are 2.241(1) and 2.303(1) angstrom, respectively. The Cu...Cu separation is 3.119(1) angstrom.