Polynuclear Gold(I) Complexes of Mercaptocarboxylic Acids

Gold(I) Thiolates, (Benzylthiolato)gold(I) Complexes, Gold(I) Mercaptocarboxylates, Polynu­ clear Gold(I) Complexes In a search for air-stable and water-soluble mercapto compounds of gold with a high gold content, benzylthiol, a-mercapto-acetic acid, /3-mercapto-propionic acid, and thiosalicylic acid were converted into aurated sulfonium salts by treatment with reagents of the type [(R^PjAufiO* BF4~ or [(R}P)Au]+ BF4~. BzSH served as a mono-functional model thiol, which was converted into BzS[Au(PMe3)]2+ BF4(1). The small tertiary phosphine was chosen in or­ der to minimize steric effects. In the crystal the cations are associated into centrosymmetrical dimers through short Au-Au contacts (auriophilicity). The two carboxylic acids with thiol functions, HSCFbCOOH and HSCH2CH2COOH, gave triply aurated species of the type {[(Ph3P)Au]2S(CH2)nCOOAu(PPh3)}+ BF4~ (2: n = 2, 3; n = 3). The crystal structure analy­ sis of the representative compound 2 showed again the presence of centrosymmetrical cation dimers with geometrical details of the sulfonium part of the molecules very similar to those of the reference compound 1. In addition, the carboxyl groups in 2 and 3 bear a (phosphine)gold unit mono-hapto bound at one of the oxygen atoms. 2-HS-C6H4-COOH was converted into a sulfonium salt {[(Ph3P)Au]2S-C6H4-COOH}+ BF4~ (4), which crystallizes free of solvent from dry dichloromethane, and as a monohydrate with one mole of dichloromethane (4a = 4 H2O CH2CI2) from hydrous CH2CI2. In the solvent-free crystalline phase (4) the cations are associated into dimers with the usual intermolecular double Au-Au contacts, but in 4a there are monomeric cations with the water molecule hydrogen-bonded to the carboxylic acid function.