Synthesen und Reaktionen von schwefelkoordinierten Ruthenium-Komplexen [1]/Syntheses and Reactions of Sulfur Coordinated Ruthenium Complexes [1]

Abstract

Abstract The syntheses and reactions of sulfur coordinated ruthenium centers with CO, PR3, (R = Me, Ø), N2H4 and N2 are investigated. Reaction of [Ru(CO)3(THF)Cl2] with lithium-o-methylthiobenzenethiolate yields cis-[Ru(CO)2(CH3S-C6H4-S)2], with Li2-o-benzenedithiolate the cis-[Ru(CO)2(C6H4S2)2]2--ion is obtained, which can be isolated either as the NMe4 salt or reacted further with 1,2-C2H4Br2 to give cis-[Ru(CO)2dttd], (dttd2-= 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane2-). In all three complexes the CO ligands are relatively inert to substitution; refluxing of [Ru(CO)2(C6H4S2)2]2- in EtOH in the presence of excess PMe3, however, and subsequent alkylation with 1,2-C2H4Br2 yields [Ru(CO)PMe3(dttd)]. [Ru(PMe3)2dttd] is obtained from [Ru(PMe3)4Cl2] and Li2-dttd, the synthesis of which is also described. In [Ru(PMe3)2(dttd)] the PMe3 ligands are inert, but in [Ru(PØ3)2(dttd)] one PØ3 ligand is easily substituted by CO or N2H4 yielding [Ru(CO)(PØ3)dttd] or [Ru(N2H4)(PØ3)dttd] respectively; [Ru(PØ3)2(dttd)] is obtained from [RU(PØ3)3Cl2] and H2-dttd. The complexes are characterized by elemental analyses, IR, 1H NMR and mass spectroscopy.