부산대학교 도서관

Addition of two equivalents of diphenylthiomethylphosphine (PPh2CH2SPh) to the starting materials [Au(tht)2]A (tht=tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M=Au, A=CF3SO3(1 a); M=Au, A=ClO4(1 b); 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 AgCF3SO3or [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.