New structural features in triphenylphosphinesilver(i) sulfanylcarboxylates

Abstract

We investigated the reactions of 1.5 : 1 : 1 mole ratio mixtures of triphenylphosphine, silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids H₂xspa 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 ¹H, ¹³C and ³¹P NMR spectroscopy. Compound 6 was also characterized by ¹³C CP/MAS, and compounds 1 and 6 by ¹⁰⁹Ag NMR spectroscopy. The crystal structures of 1, 2, 3, 4·(CH₃)₂CO, 5, 6·(CH₃)₂CO 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·(CH₃)₂CO, 5, and 6·(CH₃)₂CO are tetranuclear, and 7 mononuclear. The tetranuclear complexes contain the eight-membered coordination ring Ag₄S₂O₂ (2, 3, 4·(CH₃)₂CO, 6·(CH₃)₂CO) or the twelve-membered ring Ag₄(CO₂)₂S₂ (5).