COPPER(I) AND SILVER(I) COMPLEXES OF THE CROWN THIOETHER LIGAND 2,5,8-TRITHIA[9]-ORTHO-BENZENOPHANE (TT[9]OB) - STRUCTURES OF [CU(PPH2ME)(TT[9]OB)][CLO4] AND [AG(PPH3)(TT[9]OB)][CLO4]

The crown thioether ligand 2,5,8-trithia[9]-o-benzenophane, TT[9]OB, was prepared in 90-95% yield via the Cs+-mediated cyclization of alpha,alpha'-dibromo-o-xylene and 3-thiapentane-1,5-dithiol. This thioether ligand reacted with [Cu(CH3CN)4][ClO4] to give the Cu(I) complex [Cu(CH3CN)(TT[9]OB)][ClO4]. The coordinated acetonitrile molecule was displaced by ancillary ligands to form complexes of the formula [Cu(L)(TT[9]OB)][ClO4], where L = benzonitrile, pyridine, PPh3, or PPh2Me. The complexes were characterized by infrared spectroscopy, C-13 and H-1 NMR spectroscopy, and X-ray crystallography. The complex [Cu-(PPh2Me)(TT[9]OB)][ClO4] crystallized in the space group P1BAR with a = 12.888 (4) angstrom, b = 8.156 (2) angstrom, c = 31.575 (8) angstrom, alpha = 115.64 (2)-degrees, beta = 104.56 (2)-degrees, gamma = 99.73 (2)-degrees, V = 2745 (1) angstrom-3, and Z = 4. The structure refined to R = 4.65% anf R(w) = 5.88% for 5069 reflections with F(o)2 > 3-sigma-(F(o)2). The Cu(I) ion is in a tetrahedral geometry with the ligand TT[9]OB coordinated facially and the fourth site occupied by the PPh2Me ligand. The Ag(I) complex [Ag(PPh3)(TT[9]OB)][ClO4] was prepared directly by reacting stoichiometric amounts of AgClO4, TT[9]OB, and PPh3 in CH3CN. The complex [Ag(PPh3)(TT[9]OB)][ClO4] crystallized in the space group P2(1)/c with a = 8.1704 (8) angstrom, b = 16.239 (2) angstrom, c = 23.349 (2) angstrom, beta = 101.364 (8)-degrees, V = 3037.1 (5) angstrom-3, and Z = 4. The structure refined to R = 3.50% and R(w) = 4.59% for 2972 reflections with F(o)2 > 3-sigma(F(o)2). The Ag(I) ion is in a tetrahedral geometry with the ligand TT[9]OB coordinated facially and the fourth site occupied by the PPh3 ligand.