Oxidation of Tri-Ortho-Tolylantimony in the Presence of Peroxide, Oxygen of Air and 2,5-Dimethylbenzenesulfonic Acid. Structure of Sulfo-(μ3-Oxo)-Tris-(μ2-Oxo)-Octa-Ortho-Tolylantimony

Abstract

The interaction of tri-ortho-tolylantimony with 2,5-dimethylbenzenesulfonic acid in diethyl ether in air in the presence of tert-butyl hydroperoxide (3:2:3 mol.) synthesized sulfo-(μ₃-oxo)-tris-(μ₂-oxo)-octa-ortho-tolylantimony (1), the yield of which after recrystallization from toluene:octane mixtures (5:1 vol.) was 63 %. The X-ray diffraction pattern of crystal 1 was obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoK_α-radiation, λ = 0.71073 Å, graphite monochromator), [C₄₂H₄₂O₈SSb₃, M 1072.07, the monoclinic syngony, the symmetry group P2₁/c; cell parameters: a 11.434(5), b 21.609(11), c 18.737(8) Å, α = 90.00 degrees,
β = 104.778(14) degrees, γ = 90.00 degrees; V = 4476(4) ų; the crystal size is 1.05×0.65×0.11 mm; intervals of reflection indexes are –17 ≤ h ≤ 17, –33 ≤ k ≤ 33, –28 ≤ l ≤ 28; total reflections 125015; independent reflections 17125; R_int 0.0579; GOOF 1.044; R₁ = 0.0734, wR₂ = 0.1886; residual electron density 2.75/-1.12 e/ų] in the trinuclear complex, two atoms of antimony are hexacoordinated (CSbO 159.4(2)–165.4(3)°; OSbO 164.9(2) and 167.4(2)°), the third atom of antimony is in strongly distorted trigonal-bipyramidal coordination (axial angle OSbC 161.9(3)°, equatorial angles OSbC and OSbO vary in the interval 110.5(2)–120.8(4)°). The Sb–С, μ₂-O–Sb and μ₃-O–Sb bond lengths are 2.095(9)–2.136 (7) Å, 1.904(5)–2.165 (5) Å, and 2.008 (4)–2.387 (5) Å, respectively. The bridge bidentate sulfate ligand is bound to antimony atoms, the Sb–O_sulf. distances are 2.100(5) and 2.108(5) Å. Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (No. 1866027; deposit@ccdc.cam.ac.uk; http: //www.ccdc cam.ac.uk.).