Combination of Ph 4AsCl · H 2O, Hg(SC(O)Ph) 2 and HgCl 2 or CdCl-· 2.5H 2O in the required stoichiometric ratio gives (Ph 4As) 2[MCl 4Hg(SC(O)Ph) 2], M = Hg ( 1) or Cd ( 2). Crystals of 1 were also isolated in an unsuccessful attempt to prepare the complex (Ph 4As)[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 SHgS skeleton. The SHgS 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 [MCl 4] 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 NM R data are reported for Hg(SC(O)Ph) 2.