Treatment of silver(i) bromide with the ligands [Ph2P(Se)HNP(E)Ph2] (E = Se, S or O) and [Ph2P(Se)HNPPh2] results in the formation of the salts [{HN(Ph2PSe)2-Se,Seâ ²}2Ag]Br, [{HN(Ph2PSe)(Ph2PS)-Se,S}2Ag]Br, [{HN(Ph2PSe)(Ph2PO)-Se}2Ag]Br and [{HN(Ph2PSe)(Ph2P)-Se,P}2Ag]Br, respectively. From analysis of spectroscopic data, it appears that the [Ph2P(Se)HNP(O)Ph2] ligand is coordinated through selenium donors only. The ligand [Ph2P(Se)CH2CH2AsPh2] forms a complex [{Ph2P(Se)CH2CH2AsPh2}2Ag]Br. These products constitute the first examples of metal complexes bearing these ligands in the neutral form (protonated at the nitrogen atom). The structures of three of the complexes were determined and found to contain homoleptic, spirocyclic inorganic chelates associated with hydrogen-bonded, bridging counteranions. The compound [{HN(Ph2PSe)(Ph2PS)-Se,S}2Ag]Br underwent a transformation upon standing in solution through loss of a single [Ph2P(Se)HNP(S)Ph2] ligand to provide a bromide-bridged, neutral complex [{HN(Ph2PSe)(Ph2PS)-Se,S}AgBr]2.