Photochemical Synthesis of Ruthenium–Carbonyl Compounds with Thioether Ligands and Subsequent Oxidative Cleavage of Trinuclear Complexes by Chlorinated Solvents

The photochemical reaction of [Ru3(CO)12] with thioether ligands in THF leads to the isolation of tetranuclear ruthenium–carbonyl cluster compounds of the formula [Ru4(CO)13(μ2‐R2S)]. In these compounds, ruthenium atoms adopt a typical butterfly arrangement. If chelating ligands with two thioether functions are introduced, the reaction leads to mixtures of the trinuclear substitution products [Ru3(CO)10(RS∩SR)] and [Ru3(CO)8(RS∩SR)2]. The latter may be oxidatively cleaved by the use of chlorinated solvents to produce the mononuclear compound [Ru(CO)2Cl2(RS∩SR)] or the dinuclear complex [Ru2(CO)2(μ2‐Cl)2Cl2(RS∩SR)2] depending on the reaction conditions. Five new ruthenium–carbonyl–thioether complexes were characterized by X‐ray diffraction.