RUTHENIUM(II) COMPLEXES OF THE THIA-CYCLOPHANE LIGANDS 2,5,8-TRITHIA[9]-O-CYCLOPHANE (TT[9]OC) AND 5-OXA-2,8-DITHIA[9]-O-CYCLOPHANE (ODT[9]OC) - STRUCTURES OF RUCL2(DMSO)(TT[9]OC) AND RUCL2(PPH(3))(ODT[9]OC)

Ruthenium(II) complexes of the thiacyclophane ligands 2,5,8-trithia[9] -o-cyclophane (TT[9]OC) and 5-oxa-2,8-dithia[9]-o-cyclophane (ODT[9]OC ) were synthesized by ligand displacement reactions employing RuCl2(DM SO)(4), RuCl2(PPh(3))(3), and RuHCl(PPh(3))(3) as starting materials. X-ray crystal structures of two of these complexes, RuCl2(DMSO)(TT[9]O C) and RuCl2(PPh(3))(ODT[9]OC), demonstrate how TT[9]OC and ODT[9]OC b ind to Ru(II). RuCl2(DMSO)(TT[9]OC) crystallized as the DMSO solvate i n the orthorhombic space group Pbca with a = 19.590(5), b = 16.849(4), c = 13.149(4) Angstrom, V = 4340(3) Angstrom(3), and Z = 8. The struc ture refined to R = 5.27% and R(w) = 6.27% for 2472 reflections with F -o(2) > 3 sigma(F-o(2)). RuCl2(PPh(3))(ODT[9]OC) crystallized as a ClC H2CH2Cl solvate in the monoclinic space group P2(1)/c with a = 7.912(1 ), b = 22.419(5), c = 18.794(3) Angstrom, beta = 101.12(1), V-o = 3271 .2(9) Angstrom(3), and Z = 4. The structure refined to R = 4.96% and R (w) = 5.14% for 1800 reflections with F-o(2) > 3 sigma(F-o(2)). Both c ompounds are octahedral with the thiacyclophane ligand bound through t hree donor atoms in a facial coordination mode, cis chlorine atoms, an d the unique ancillary ligand, DMSO or PPh(3), bound trans to the cent ral S or O donor of the macrocycle. The X-ray structures support H-1 N MR spectral evidence which shows that the ligands are bound in an ''en do'' mode for L = DMSO and in an ''exo'' mode when L = PPh(3). The rea ction of RuHCl(PPh(3))(3) with TT[9]OC yields the ruthenium hydride co mplex RuHCl(PPh(3))(2)(TT[9]OC). H-1 and P-31 NMR spectroscopy are con sistent with an octahedral species for which the macrocycle occupies o nly two coordination sites acting as a bidentate eta(2)-chelating liga nd.