Diphenyl(l-pyridyl)phosphine Sulfide as a Ligand in Mono- and Binuclear Coinage Metal Complexes

D iphenyl(l-pyridyl)phosphine sulfide, Ph2pyPS, 1, gives a 1:1 complex (2) with AuCl upon treatm ent with (C4HsS)AuCl. According to an X-ray diffraction analysis, this com ­ pound is isom orphous with the Ph^PS complex. [Ph3PAu]BF4 and 1 give the cationic com plex [Ph;?PAuSPpyPh2]BF4 (3 ) . With two equivalents o f the same reagent the binuclear com plex 4 is generated, in which the metal atoms are Sand N-bonded. The reaction o f 2 equivalents o f 1 with [(tetrahydrothiophene)2A u]C 104 affords the 2:1 complex 5 with the gold atom exclusively S-bonded. The analogous reaction with AgBF4 gives the 2:1 complex 6, the structure o f which has also been determined by X-ray diffraction. The silver atom is engaged in coordinative bonding with both sulfur and both nitrogen atoms in a quasi-tetrahedral environm ent. Addition o f A gC 104 to com pound 5, and of [(M eCN)4C u]BF4 to 6, gives m ixed-m etal com plexes (7, 8) with head-to-head structures, the silver atoms being exclusively S-bonded.