168561-63-5Relevant academic research and scientific papers
Ruthenium(II) complexes of the thiacyclophane ligands 2,5,8-trithia-o-cyclophane (TTOC) and 5-oxa-2,8-dithia-o-cyclophane (ODTOC). Structures of RuCl2(DMSO)(TTOC) and RuCl2(PPh3)(ODTOC)
Groot, Broer de,Jenkins, Hilary A.,Loeb, Stephen J.,Murphy, Shannon L.
, p. 1102 - 1110 (2007/10/03)
Ruthenium(II) complexes of the thiacyclophane ligands 2,5,8-trithia-o-cyclophane (TTOC) and 5-oxa-2,8-dithia-o-cyclophane (ODTOC) were synthesized by ligand displacement reactions employing RuCl2(DMSO)4, RuCl2(PPh3)3, and RuHCl(PPh3)3 as starting materials.X-ray crystal structures of two of these complexes, RuCl2(DMSO)(TTOC) and RuCl2(PPh3)(ODTOC), demonstrate how TTOC and ODTOC bind to Ru(II).RuCl2(DMSO)(TTOC) crystallized as the DMSO solvate in the orthorhombic space group Pbca with a=19.590(5), b=16.849(4), c=13.149(4) Angstroem, V=4340(3) Angstroem3, and Z=8.The structure refined to R=5.27percent and RW=6.27percent for 2472 reflections with Fo2>3?(Fo2).RuCl2(PPh3)(ODTOC) crystallized as a ClCH2CH2Cl solvate in the monoclinic space group P21/c with a=7.912(1), b=22.419(5), c=18.794(3) Angstroem, β=101.12(1) deg, V=3271.2(9) Angstroem3, and Z=4.The structure refined to R=4.96percent and RW=5.14percent for 1800 reflections with Fo2>3?(Fo2).Both compounds are octahedral with the thiacyclophane ligand bound through three donor atoms in a facial coordination mode, cis chlorine atoms, and the unique ancillary ligand, DMSO or PPh3, bound trans to the central S or O donor of the macrocycle.The X-ray structures support 1H NMR spectral evidence which shows that the ligands are bound in an endo mode for L=DMSO and in an exo mode when L=PPh3.The reaction of RuHCl(PPh3) with TTOC yields the ruthenium hydride complex RuHCl(PPh3)2(TTOC). 1H and 31P NMR spectroscopy are consistent with an octahedral species for which the macrocycle occupies only two coordination sites acting as a bidentate η2-chelating ligand.Key words: thioether, macrocycle, hydride, crystal structure.
