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 bis ligand complexes [M{MeC(CH2ER)3}2][PF6]2.
The crystal structure of [Pt{MeC(CH2SeMe)3}2][PF6]2 (C16H36F12P2PtSe6, a = 12.272(10) Å, b = 18.563(9) Å,
c = 15.285(7) Å, β = 113.18(3)°, monoclinic, P21/n, Z = 4) confirms distorted square planar Se4 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][CF3SO3]2 and [Ru{MeC(CH2TePh)3}2][CF3SO3]2 are obtained from [Ru(dmf)6][CF3SO3]3 and tripod ligand in EtOH
solution. The thioether complex (C18H36F6O6RuS8, a = 8.658(3) Å, b = 11.533(3) Å, c = 8.659(2) Å, α =
108.33(2)°, β = 91.53(3)°, γ = 106.01(2)°, triclinic, P1̄, 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 d6 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) Å, b = 15.374(3)
Å, c = 14.071(2) Å, β = 93.86(2)°, monoclinic, P21/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.