A straightforward and generalizable synthetic methodology for the synthesis of ruthenium(ii) complexes with thioether ligands from either Ru(iii) or Ru(0) precursors

摘要

The reaction of Ru_3(CO)_(12) in chloroform with thioether ligands after 25 min of irradiation leads to the formation of mononuclear ruthenium(ii) complexes of the general formula fac-[Ru(CO) _3Cl_2(S)] (S = thioether) if monodentate ligands are introduced. In the case of chelating bidentate thioethers a complex of the formula all-cis-[Ru(CO)_2Cl_2(S∩S)] is produced. If irradiation time is prolonged to 2.5 h mononuclear complexes of the composition trans-[RuCl_2(S)_4] or trans-[RuCl_2(S∩S) _2] are observed. The use of tetrahydrothiophene (THT) in the latter case produces a dinuclear ruthenium(ii) complex of the formula [Ru _2(CO)_2Cl_4(THT)_2(μ-THT) _2] which is the first structurally characterized neutral ruthenium complex with a bridging thioether ligand. Regardless of the used ligand complexes trans-[RuCl_2(S)_4] or trans-[RuCl _2(S∩S)_2] are formed from the reaction of RuCl _3·3H_2O with the corresponding thioether in the presence of NEt_3 and formaldehyde in excellent yields. Six new ruthenium complexes are characterized by X-ray diffraction.