Synthesis, spectroscopic, and structural studies on transition metal complexes involving homoleptic tripodal selenoether and telluroether coordination

The reaction of [MCl2(NCMe)(2)] (M = Pd or Pt) with 2 molar equiv of MeC(CH2ER)(3) (E = Se, R = Me; E = Te, R = Me or Ph) and 2 molar equiv of TlPF6 affords the his ligand complexes [M{MeC(CH2ER)(3)}(2)][PF6](2). The crystal structure of [Pt{MeC(CH2SeMeMe)(3)}(2)][PF6](2) (C16H36F12P2PtSe6, a = 12.272(10) Angstrom, b = 18.563(9) Angstrom, c 15.285(7) Angstrom beta = 113.18(3)degrees monoclinic, P2(1/n), Z = 4) confirms distorted square planar Se-4 coordination at Pt(II), derived from two bidentate tripod selenoethers with the remaining arm not coordinated and directed away from the metal center. Solution NMR studies indicate that these species are fluxional and that the telluroether complexes are rather unstable in solution. The octahedral bis tripod complexes [Ru{MeC(CH2SMe)(3)}(2)][CF3-SO3](2) and [Ru{MeC(CH2TePh)(3)}(2)][CF3SO3](2) are obtained front [Ru(dmf)(6)][CF3SO3](3) and tripod ligand in EtOH solution. The thioether complex (C18H36F6O6RUS8 a = 8.658(3) Angstrom, b = 11.533(3) Angstrom, c 8.659(2) Angstrom, alpha = 108.33(2)degrees, beta = 91.53(3)degrees, gamma 106.01(2)degrees triclinic, P1, Z = 1) is isostructural with its selenoether analogue, involving two facially coordinated trithioether ligands in the syn configuration. NMR spectroscopy confirms that this configuration is retained in solution for all of the bis tripod Ru(II) complexes. These low-spin d(6) complexes show unusually high ligand field splittings. The hexaselenoether Rh(III) complex [Rh{MeC(CH2SeMe)(3)}(2)][PF6](3) was obtained by treatment of [Rh(H2O)(6)](3+) with 2 molar equiv of MeC(CH2SeMe)(3) in aqueous MeOH in the presence of excess PF6- anion, while the iridium(III) analogue [Ir{MeC(CH2SeMe)(3)}(2)][PF6](3) was obtained via the reaction of the Ir(I) precursor [IrCl(C8H14)(2)](2) with the selenoether tripod in MeOH/aqueous HBF4. NMR studies reveal different invertomers in solution for both the Rh and Ir species. The Cu(I) complexes [Cu{MeC(CH2ER)(3)}(2)]PF6 were obtained from [Cu(NCMe)(4)]PF6 and tripod ligand in CH2Cl2 solution. The corresponding Ag(I) species [Ag({MeC(CH2TeR)(3)}(2)]CF3SO3 (R = Me or Ph) were obtained from Ag[CF3SO3] and tripod telluroether. In contrast, a similar reaction with 2 molar equiv of MeC(CH2SeMe)(3) afforded only the 1:1 complex [Ag{MeC(CH2SeMe)(3)}]CF3SO3. The structure of this species (C9H18AgF3O3SSe3, a = 8.120(3) Angstrom, b = 15.374(3) Angstrom, c = 14.071(2) Angstrom, beta = 93.86(2)degrees, monoclinic, P2(1/n), Z = 4) reveals a distorted trigonal planar geometry at Ag(I) derived from one bidentate selenoether and one monodentate selenoether. These units are then linked to adjacent Ag(I) ions to give a one-dimensional linear chain cation.