Synthesis, structure, and multi-NMR studies of (Me4N)[A{M(SC{O}Ph)3}2] (A = Na, M = Hg; A = K, M = Cd or Hg)

Abstract

The compounds (Me4N)[A{M(SC{O}Ph)3}2] (A = K, M = Cd (2); A = Na, M = Hg (3); and A = K, M = Hg (4)) were synthesized by reacting the appropriate metal chloride with A+PhC{O}S- and Me4NCl in the ratios 1:3:1 and 2:6:1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. All the compounds are isomorphous, isostructural, and crystallized in the space group P1̄ with Z = 1. Single-crystal data for 2: a = 10.6670(2) Å, b = 11.1522(2) Å, c = 11.9294(2) Å, α = 71.782(1)°, β = 85.208(1)°, γ = 69.418(1)°, V = 1261.40(4) Å3, D(calc) = 1.528 g cm-3. Single-crystal data for 3: a = 10.840(2) Å, b = 10.946(4) Å, c = 12.006(3) Å, α = 72.18(2)°, β = 86.75(2)°, γ = 67.43(2)°, V = 1249.3(6) Å3, D(calc) = 1.756 g cm-3. Single-crystal data for 4: a = 10.4780(1) Å, b = 11.2563(2) Å, c = 11.9827(2) Å, α = 71.574(1)°, β = 85.084(1)°, γ = 70.705(1)°, V = 1265.23(3) Å3, D(calc) = 1.755 g cm-3. In the [A{M(SC{O}Ph)3}2]- anions, each M(II) atom is bonded to three thiobenzoate ligands through sulfur atoms, giving a trigonal planar MS3 geometry. The carbonyl oxygen atoms from the two [M(SC{O}Ph)3]- anions are bonded to the alkali metal atom, providing an octahedral environment. Solution metal NMR studies showed the concentration-dependent dissociation of the alkali metal ions in the trinuclear anions.