Thiolates bridging ligands

The best enantioselectivity (35% ee) was observed in the reaction of l-(l-naphthyl)-2-propyn-l-ol with acetone in the presence of a complex bearing a 1-naphthylethylthio-lato moiety as a chiral ligand. Although the enantioselectivity is not yet satisfactory, this was the first example of an enantioselective propargylic substitution reaction catalyzed by transition metal complexes [27]. It is noteworthy that the chiral thiolate-bridged ligands work to control the chiral environment around the diruthenium site. 

Thiolates (RS ) represent an extensive family of ligands, and include chelating forms. Thiolates are known to act as monodentate donors, but often act in a bridging role. There is a clear biological interest, through participation of thiolates (cysteine residues) as donors in many metalloproteins both as terminal S donors and bridging ligands in, for example, Fe S clusters. 

The reaction of thiolate ligands with [Ni(terpy)Cl2] in MeOH or MeCN affords different products depending on the basicity and bulk of the thiolate ligand employed. Thus, the reaction with PhSH yields the thiolate bridged dimer [Ni(terpy)(SPh)2]2-6CH3OH (281), reaction with C6F5SH yields the... 

Thiolate ligands also afford an interesting variety of species [156-161]. Because or their relation with the antiarthritic drug Auranofin, thiolate-goldphosphine derivatives have received great interest. The simplest structures are those in which the thiolate bridges two gold atoms and thus different compounds of stoichiometry... 

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