Mercury(II) and methylmercury(II) complexes of novel sterically hindered thiolates: 13C and 199Hg NMR studies and the crystal and molecular structures of [MeHg(SC6H2-2,4,6-Pri3)], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg{(2-SC6H4)2SiMe2}]2

Several series of complexes of the types [MeHg(SR)] and [Hg(SR)2] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed 1H, 13C, and 199Hg NMR studies revealed several general trends. The 199Hg chemical shifts moved upfield in the order [MeHg(SR)] < [Hg(SCR'R double-prime R'double-prime)2] < [Hg(S-aryl)2] < [Hg(S-pyridyl)2]. For the [MeHg(SR)] series of complexes, 1J(Hg-C) correlates with δ(13C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ(199Hg) with steric cone angles for a subset of the complexes. Crystal data for the complexes are reported. 86 refs., 7 figs., 11 tabs