SYNTHESIS, NMR (C-13, CD-111 HG-199) SPECTRA AND STRUCTURES OF (PH4AS)(2)[HG2CL4(SC(O)PH)(2)] AND (PH4AS)(2)[CDCL4HG(SC(O)PH)(2)]

Combination of Ph4AsCl . H2O, Hg(SC(O)Ph)(2) and HgCl2 or CdCl2 . 2.5H (2)O 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)degrees in 1 and 175.4(1)degree s in 2. In each, the Hg(SC(O)Ph)(2) moiety is involved in weak interac tions with two chlorine atoms from [MCl4](2-). Mercury-199 and Cd-111 NMR spectral studies indicate that the Hg(SC(O)Ph)(2) remains intact i n solution, and that scrambling or transfer of ligands between the lin ear and tetrahedral metal centres does not occur. Carbon-13 and Hg-199 NMR data are reported for Hg(SC(O)Ph)(2). (C) 1998 Published by Elsev ier Science Ltd. All rights reserved.