Addition of Alkynes and Alkeaes to ReS_4~-: Reactivity Akin to OsO_4

摘要

The fetrathiometallates, anions of the formula MS_4~(n-), represent one of the most fundamentally important classes of soluble metal sulfides. In the course of our studies on thiometallates, we noticed that the complex (MeC_5H_4)Ru(dppe)-SReS_3 is reactive toward alkenes. This is not very surprising since unsaturated organic compounds are known to add to a variety of organometallic sulfido compounds as well as the cluster Mo_3S_4(H_2O)_9~(4+4). A series of control experiments demonstrated however that ReS_4~- itself is highly reactive toward a wide range of unsaturated organic substrates-this is significant since simple thiometallates were not thought, to be reactive toward unactivated alkynes and alkenes. Additionally, the new transformations define routes from simple precursors to oxo(or sulfido)-dithiolene complexes that resemble the active sites of several Mo- and W-containing enzymes, the structures of which have recently been determined.