Syntheses, spectroscopic (R, H-1 and P-31 NMR) and some 'low'-temperature single-crystal X-ray structural characterizations are reported for a wide variety of adducts of AgX:PPh(2)py (:S) (n:m(:x)) (X = Cl, Br, I, NO2, SCN, ClO4, BF4, O2CCF3 (tfa), O2CCH3 (ac), O2CC3R7 (hefb), S2CN(C2H5)(2) (dtc), 1/2 SO42-; PPh(2)py = L = diphenyl-2-pyridylphosphine) stoichiometry. All compounds are binuclear, a wide range of (AgAg)-Ag-... distances being found, bridging entities being diverse, either anionic X or the P,N-ambidentate ligand PPh(2)py. PPh(2)py acts as a terminal P-donor in Agdtc: PPh(2)py (1:1)(2) and in [(Ph(2)py)(2)Ag([mu-Cl)(2)Ag(PPh(2)py)(NCMe)], but fully utilizes its coordinating capabilities in [(MeCN)Ag(mu-PPh(2)py)(3)Ag(OHI2)](ClO4)(2) and [(NO2)Ag(p-PPh(2)py)(2)Ag(O2N)]. Comparison is made between the latter compound and the analogous species [(NO2)Ag(mu-PPh(2)bim)(2)Ag(O2N)] (PPh(2)bim=L'=1-benzyl-2-imidazolyldiphenylphosphine). (c) 2005 Elsevier B.V. All rights reserved.