Synthesis and photochemical study of Cu(I) complexes with tri- p-tolylphosphine and heterocyclic thiones. The crystal structure of [CuCl(pymtH)( p-CH 3C 6H 4) 3P] 2

Abstract

Reactions of [Cu(tptp)X] 4 (tptp=tri- p-tolyl-phosphine, XCl, Br or I) 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(tptp)(L)X] 2. The complexes have been characterized by elemental analyses, IR, UV-Vis and 1H NMR spectroscopy. The photochemical behaviour of these complexes in chloroform solutions has been investigated. Irradiation causes the release of the phosphine and the formation of dinuclear compounds containing a Cu 2S 2 core. The crystal structure of [Cu(tptp)(pymtH)Cl] 2 has been determined by single-crystal X-ray diffraction methods. The red crystals are triclinic, space group P 1 with a=19.512(2), b=10.388(3), c=14.474(2) Å, α=99.00(2), β=73.28(1), γ=116.22(2)°, D calc=1.394 M m −3, V=1228.2(4) Å 3 and Z=1. The molecule contains a planar Cu 2S 2 moiety with CuS bond lengths of 2.356(1) and 2.470(1) Å. The CuP and CuCl distances are 2.227(1) and 2.300(1) Å, respectively. The Cu···Cu separation is 3.316(0) Å.