Synthesis and structural characterization of adducts of silver (I) diethyldithiocarbamate with P-donor ligands

Adducts of triorganophosphines PR3, and diphosphines R2P(CH2)(n)PR2 with silver(I) diethyldithiocarbamate Ag(dtc) have been synthesized and characterized both in solution (H-1, P-31 NMR) and in the solid state (IR, single-crystal X-ray structure analysis). The topology of the structures in the solid state was found to depend on the nature of the P-donor and on the Ag(dtc):P-donor stoichiometric ratio. In the mononuclear [(Ph2MeP)(2)Ag(dtc)] and [{(:CH.PPh2)(2)}Ag(dtc)], four-coordinate P2AgS2 environments are found, as also in [(dtc)Ag(P'-dppm-P')(2)Ag(dtc)] where the two Ag(dtc) moieties are linked by the pair of bidentate, bridging, dppm ligands; by contrast the dppp adduct Ag(dtc):dppp (1:1) is an infinite one-dimensional polymer. In the other complexes [(R3P)Ag(dtc)](2) structurally defined, the silver environment is PAgS3, two of the sulfur atoms drawn from the same dtc, now an unsymmetrical chelate, and one of the sulfur atoms bridged to the second silver atom. (C) 2007 Elsevier B.V. All rights reserved.