Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions

Addition of two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht = tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM'(PPh2CH2SPh)2](CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(C6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO3 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH2SPh)2]CF3SO3 (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh2CH2SPh)2-(CF3CO2)2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5) (CF3CO2)2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.