Abstract Diphenyl(1-pyridyl)phosphine sulfide, Ph2pyPS, 1, gives a 1:1 complex (2) with AuCl upon treatment with (C4H8S)AuCl. According to an X -ray diffraction analysis, this compound is isomorphous with the Ph3PS complex. [Ph3PAu]BF4 and 1 give the cationic complex [Ph3PAuSPpyPh2]BF4 (3 ) . With two equivalents of the same reagent the binuclear complex 4 is generated, in which the metal atoms are S- and N-bonded. The reaction of 2 equivalents of 1 with [(tetrahydrothiophene)2Au]ClO4 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 of 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 environment. Addition of AgClO4 to com pound 5, and of [(MeCN)4Cu]B F4 to 6, gives mixed-metal complexes (7, 8) with head-to-head structures, the silver atoms being exclusively S-bonded.
Front Cover: Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase (Chem. Asian J. 21/2019)