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

Abstract

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. © 1998 Published by Elsevier Science Ltd. All rights reserved.