Synthesis, NMR (13C, 111Cd, 199Hg) spectra and structures of (Ph4As)2[Hg2Cl4(SC(O)Ph) 2] and (Ph4As)2[CdCl4Hg(SC(O)Ph)2]

Article abstract of DOI:10.1016/S0277-5387(97)00530-5

Combination of Ph₄AsCl · H₂O, Hg(SC(O)Ph)₂ and HgCl₂ or CdCl₂ · 2.5H₂O in the required stoichiometric ratio gives (Ph₄As)₂[MCl₄Hg(SC(O)Ph)₂], M = Hg (1) or Cd (2). Crystals of 1 were also isolated in an unsuccessful attempt to prepare the complex (Ph₄As)[Na{Hg(SC(O)Ph)₃}₂]. X-ray crystallographic analyses of 1 and 2 show both to contain a Hg(II) bonded to two thiobenzoate ligands with a near-linear S - Hg - S skeleton. The S - Hg - S angle is 174.9(2)° in 1 and 175.4(1)° in 2. In each, the Hg(SC(O)Ph)₂ moiety is involved in weak interactions with two chlorine atoms from [MCl₄]^2-. Mercury-199 and ¹¹¹Cd NMR spectral studies indicate that the Hg(SC(O)Ph)₂ remains intact in solution, and that scrambling or transfer of ligands between the linear and tetrahedral metal centres does not occur. Carbon-13 and ¹⁹⁹Hg NMR data are reported for Hg(SC(O)Ph)₂.