Two-, three- and four-coordinate silver(I) complexes, AgX (X = CN-, PF6-, and SbF6-), with triphenyl phosphine, tricyclohexyl phosphine, cliphenylcyclohexyl phosphine, and clicyclohexylphenyl phosphine have been synthesised and characterised by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, and C-13 and P-31 NMR spectroscopy. From the reaction of a metal salt to phosphine ligand ratio of 1: 1 the various compounds crystallize as 1:2,13, and 1:4 compounds [Ag(PPh2CY)(3)(CN)]center dot 5H(2)O (1), [Ag(P-CY3)(2)]center dot PF6 (2), [Ag(PPh3)(4))]SbF6]CHCl3 (3). [Ag(PCY3)(2)]center dot SbF6 (4), [Ag(PPh2CY)(2)(C3H6O)]center dot SbF6 (5), and [Ag(PPhCY2)(2)]center dot SbFG center dot CHCl3 (6) monomers, with a wide variety of geometries around the central silver(I) atom. Compounds I and 3 have slightly distorted tetrahedral geometry around the silver(I) atom. The compounds 2, 4, and 6 show linear geometry around the metal centre, while compound 5 has a distorted trigonal planar geometry. The elemental analysis and NIVIR spectroscopic results are consistent with the single crystal structural analyses. (C) 2009 Elsevier Ltd. All rights reserved.