SYNTHESIS AND PHOTOLYSIS OF A NEW SERIES OF CU(I) COMPLEXES WITH TRI-ORTHO-TOLYLPHOSPHINE AND HETEROCYCLIC THIONES AS LIGANDS - THE CRYSTAL-STRUCTURE OF (THIAZOLIDINE-2-THIONE)(TRI-O-TOLYLPHOSPHINE)-COPPER(I)BROMIDE

Reactions of [Cu(totp)Br]4 (totp = tri-omicron-tolyl-phosphine) 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 (bzimtH2) and quinoline-2-thione (qntH) afford mononuclear complexes of the general formula [Cu(totp)(L)Br]. The complexes have been characterized by elemental analyses and their IR, UV-Vis and H-1 NMR spectroscopic data. The photolysis in chloroform solutions of these complexes has also been investigated. A single-crystal X-ray diffraction study was carried out on the tzdtH complex [Cu(totp)(tzdtH)Br]. The pale yellow compound crystallizes in the triclinic space group P1BAR with a = 9.4672(7), b = 10.9818(8), c = 14.293(1) angstrom, alpha = 93.059(2), beta = 67.912(2), gamma = 118.208(2)-degrees, D(calc) = 1.570 Mg m-3, V = 1199.23(9) angstrom 3 and Z = 2. The complex exhibits an approximate trigonal planar CuSPBr core with Cu-S 2.290(1), Cu-P 2.256(1) and Cu-Br 2.413(0) angstrom. The actual structural type appears to depend upon the identity of the phosphine ligand which has a decreased flexibility because of the steric demands of the ortho positioned methyl groups.