MERCURY(II) AND METHYLMERCURY(II) COMPLEXES OF NOVEL STERICALLY HINDERED THIOLATES - C-13 AND HG-199 NMR-STUDIES AND THE CRYSTAL AND MOLECULAR-STRUCTURES OF [MEHG(SC6H2-2,4,6-PRI3)], [HG(SC6H4-2-SIME3)2], [HG(2-SC5H3N-3-SME3)2], AND [HG(2-SC6H4)SIME2)]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″R‴)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 are as follows. [CH3Hg(SC6H2-2,4,6·Pri3)]: triclinic [formula omited], a = 5.962 (1) Å, b = 9.649 (1) Å, c = 15.951 (2) Å, a = 79.60 (1)°, β = 79.58 (1)°, γ = 84.68 (1)°, V= 886.1 (10) Å3, Z = 2, Dcalc = 1.69 g cm-3. Structure solution and refinement based on 2115 reflections (Mo Kα; λ = 0.71073 Å) converged at R = 0.0497. [Hg-(SC6H4-2-SiMe3)2]: monoclinic A2/a, a = 6.900 (1) Å, b = 12.856 (2) Å,c = 25.974 (5) Å, β = 104.20 (1)°, V= 2234.1 (11) Å3, Z = 4, Dcalc = 1.67 g cm-3, 1277 reflections, R = 0.0313. [Hg(2-SC5H3N-3-SiMe3)2]: triclinic [formula omited], a = 9.058 (2) Å, b = 9.982 (2) Å, c = 12.639 (3) Å, α = 82.15 (1)°, β = 71.65 (2)°, γ = 79.98 (2)°, V= 1064.3 (10) Å3, Z = 2, Dcalc. = 1.77 g cm-3, 3233 reflections, R = 0.0850. [Hg{(2-SC6H4)2SiMe2}]2: triclinic [formula omited], a = 8.680 (2) Å, b = 12.705 (3) Å, c = 15.053 (4) Å, α = 73.94 (2)°, β = 77.56 (2)°, γ = 70.85 (2)°, Z = 2, Dcalc = 2.12 g cm-3, 1350 reflections, R = 0.0854. © 1990, American Chemical Society. All rights reserved.