Twenty-one adducts of the form AgNO3:ER3:L (1: 1: 1) (E = P, As, Sb; R = Ph, cy, o-tolyl, mes; L = 2,2'-bipyridyl ('bpy')-based ligand), together with AgNO3:Pcy(3):tPY (2:2:1) and AgNO3:PPh3:tPY (1:2:1) ('tpy' (2,2':6,2"-terpyridine)), have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, H-1 and P-31 NMR) and single crystal X-ray diffraction studies. The resulting com plexes are predominantly of the form [(R3E)AgL]+NO3-, with trigonal EAgN2 coordination environments, the planarity of which is perturbed by the approach of the nitrate anion. The nitrate ion shows uni- or (semi-)bidentate coordination, excepting the complex AgNO3:P(o-tol)(3):doca (1: 1: 1) (dpca = bis(2-picolyl)amine) where the anion is uncoordinated, the donor dpca being a pincer-tridentate. The complex AgNO3:Pcy(3):tpy (2:2:1), also reported, is dinuclear with a bridging unidentate nitrate and a terpyridine, the latter bridging through its central ring, with the peripheral rings forming chelates to either side, whereas the complex AgNO3:PPh3:tpy (1:2:1) is ionic with a five-coordinate silver, bonded to tridentate tpy and two phosphines. (c) 2006 Elsevier B.V. All rights reserved.