New structural features in triphenylphosphinesilver(I) sulfanylcarboxylates

We investigated the reactions of 1.5 : 1 : 1 mole ratio mixtures of triphenylphosphine, silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids H(2)xspa in chloroform/water, where in the acid nomenclature, spa = 2-sulfanylpropenoato and x = p, Clp, mp, diBr-o-hp or f with p = 3- phenyl-, Clp = 3-( 2-chlorophenyl)-, mp = 3- methoxyphenyl-, diBr-o-hp = 3-( 3,5-dibromo-2-hydroxyphenyl)- and f = 3-(2-furyl)-. The compounds [Ag(PPh3)(Hpspa)]( 1), [(AgPPh3)(2)(xspa)] [ x = Clp ( 2), o-mp ( 3), p-mp ( 4), diBr-o-hp ( 5) and f ( 6)] and [Ag(PPh3)(3)( Hfspa)] ( 7) were isolated and all except 7 were characterized by IR, Raman and FAB mass spectrometry and by H-1, C-13 and P-31 NMR spectroscopy. Compound 6 was also characterized by C-13 CP/MAS, and compounds 1 and 6 by Ag-109 NMR spectroscopy. The crystal structures of 1, 2, 3, 4 center dot(CH3)(2)CO, 5, 6 center dot(CH3)(2)CO and 7 were determined by X-ray diffraction. 1 has a supramolecular structure based on hydrogen bonding between dinuclear units, and all the other complexes adopt discrete structures. 2, 3, 4 center dot(CH3)(2)CO, 5, and 6 center dot(CH3)(2)CO are tetranuclear, and 7 mononuclear. The tetranuclear complexes contain the eight-membered coordination ring Ag4S2O2 (2, 3, 4 center dot(CH3)(2)CO, 6 center dot(CH3)(2)CO) or the twelve-membered ring Ag-4(CO2)(2)S-2 (5).