Novel solvated forms are spectroscopically (H-1, C-13, (31)p, IR and conductivity studies) and structurally described for diverse silver oxyanion salt:bis(diphenylphosphino)-ligand adducts of 2:1:n (AgX:dppx:S) stoichiometry. AgClO4:dppf-MeCN (2:1:4) ('dppf' = bis(diphenylphosphino)ferrocene) is a binuclear centrosymmetric species: [(O3ClO)(MeCN)(2)Ag(P-dppf-P')Ag(NCMe)(2)(OClO3)], Ag-P short at 2.368(1) angstrom. Two MeOH/H2O solvates are described, of AgX:dppp (2: 1) stoichiometry, both single stranded polymers (X = carboxylate: 'ac' = acetate, 'tfa' = trifluoroacetate; 'dppp' = Ph2P(CH2)(x)PPh,; x = 3), with silver atoms spanned alternately by: (i) a P-dppp-P' bridge, supported by tenuously bridging water or methanol, and (ii) O-ac, tfa-O' bridge(s), being assigned stoichiometries Agtfa:dppp:H2O (2:1:1) (.) MeOH and Agac:dppp:MeOH(2:1:0.5) (,) 31/2H(2)O.The structure of AgCIO4:dppe:MeCN (1:1:1) ('dppe', 2 x = 2). also a one-dimensional polymer, but with all Ag...Ag sequences bridged by the P,P' ligand, and with unidentate MeCN and OCIO3 coordinated to the silver, is also recorded. (c) 2005 Elsevier B.V.. All rights reserved.