Coordination chemistry of sterically hindered thiolate ligands. Preparation and structural characterization of the oligomeric homoleptic complexes [o-trimethylsilylbenzenethiolato]copper dodecamer and [o-trimethylsilylbenzenethiolato]silver octamer and a

The ligand 2-(trimethylsilyl)benzenethiol may be prepared by treatment of 2-(phenylthio)tetrahydropyran with tert-butyllithium in THF/HMPA at -90 °C followed by chlorotrimethylsilane and then mercuric chloride/hydrogen sulfide. Alternatively, conversion of thiophenol to lithium 2-lithiobenzenethiolate followed by quenching at -78 °C with an equivalent of chlorotrimethylsilane affords the ligand 2-(trimethylsilyl) benzenethiol. A cadmium salt of structure (Et4N)₂[Cd(SC₆H₄-o-SiMe₃)₄] (I) (as determined by X-ray crystallography) and copper and silver salts of structures [Cu(SC₆H₄-o-SiMe₃)]i₂(II) and [(Ag-(SC₆H₄-o-SiMe₃)}₄]₂(III), respectively, can be prepared from reactions of the ligand with the appropriate metal precursors. Crystal data for [Cu(SC₆H₄-o-SiMe₃)]₁₂: monoclinic space group P2₁/n with a = 17.219 (2) Å, b = 30.563 (4) Å, c = 27.446 (3) Å, β = 93.58 (2)°, V = 14416.0 (18) ų, and Z = 4; structure solution and refinement based on 5645 reflections with F₀≥ 6σ(F₀) to give R = 0.064. Crystal data for [{Ag(SC₆H₄-o-SiMe₃)}₄]₂: monoclinic space group A2 with a = 11.923 (2) Å, b - = 14.761 (2) Å, c = 26.618 (4) Å, β = 98.30 (1)°, V = 4635.6 (12) ų, and Z= 4; structure solution and refinement based on 2954 reflections with F₀≥ 6σ(F_°) to give R = 0.062. Crystal data for (Et₄N)₂[Cd(SC₆H4-o-SiMe₃)4]: hexagonal space group p6₁22 with a = b = 17.501 (3) Å, c = 39.100 (5) Å, V = 10371.3 (18) ų, and Z = 6; structure solution and refinement based on 1991 reflections with F₀≥6σr(F₀) to give R = 0.0675.