Ethereal Hydroperoxides: Powerful Reagents for S-Oxygenation of Bridging Thiophenolate Functions

S-Oxygenation of thiophenolate bridges by ethereal hydroperoxides was studied. [Ni^II₂L^S(PhCO₂)]⁺ (1), where L^S = macrocyclic aminethiolate supporting ligand, is S-oxygenated readily in a mixed methanol/acetonitrile solution with ether/dioxygen at room temperature in the presence of daylight. The reactions were found to depend strongly on the choice of the ether. Uptake of two O atoms occurs in dioxane to give a mixed thiolate/sulfinate complex [Ni^II₂L^SO(PhCO₂)]⁺ (2) containing the rare five-membered Ni(μ_1,1-S)(μ_1,2-OS)Ni core. In tetrahydrofuran, four O atoms are taken up by 1 to generate the bis(sulfinate) species [Ni^II₂L^SO(PhCO₂)]⁺ (3). A mono-S-oxygenated sulfenate intermediate can be detected by electrospray ionization mass spectrometry. The oxygenation reactions proceed in high yields without complex disintegration and invariably provide μ_1,2-bridging sulfinates as established by spectroscopy (IR and UV/vis), X-ray crystallography, and accompanying density functional theory calculations. The oxygenation of the S atoms has a strong impact on the electronic structures of the nickel complexes. The monosulfinate complex 2 has an S = 2 ground state resulting from moderate ferromagnetic exchange coupling interactions (J = +15.7 cm^-1; H = -2JS₁S₂), while an antiferromagnetic exchange interaction in 3 shows the presence of a ground state with spin S = 0 (J = -0.56 cm^-1).