Abstract: | Contributions to the Chemistry of Silicon-Sulfur Compounds. XXXV. The Dimeric Thallium(I)-tri-tert-butoxysilanethiolate Thallium(I)-tri-tert-butoxysilanethiolate is formed as a dimer by reaction of tri-tert-butoxysilanethiol with TlNO3. The compound crystallizes as colourless triclinic plates. F.I. mass spectra show only the mass of the dimeric species (m/e = 968), in the E.I. mass spectra, however, also the peak for the monomeric unit (m/e = 484) is observed. The molecule is of 1 /Ci symmetry. The central four-membered ring is plane, the bond distances and angles therein are d (Tl? S) = 289 pm and S/Tl/S = 91.5°. The Tl atoms are additionally coordinated by an oxygen atom of the tri-tert-butoxysilyl group (d(Tl? O) = 280 pm). The mean bond angle at the threebonded sulfur atom was found to be 90° (d(S? Si) = 207.8 pm). Related details of the structure are discussed (space group P1 ; a = 927.5 pm, b = 1395.1 pm, c = 882.1 pm; α = 108.43°, β = 116.77°, γ = 90.98°; Z = 2; R = 0.032; 2887 reflections hkl). |