Crystallization of 12 silver(I) halide/pseudo halide1,3-bis(diphenylphosphino)propane (dppp) mixtures from acetonitrile have resulted in the isolation of a novel series of neutral complexes, [AgX(dppp-P,P)(dppp-P)] (X = Cl, Br, I or CN) containing co-ordinated anion and uni- and bi-dentate dppp ligands. In contrast, the thiocyanate and nitrate complexes precipitate as ionic [Ag(dppp-P,P)2]X with unco-ordinated anion and bidentate phosphine ligands, a structural type previously found for other 12 silver(I)diphosphine complexes. The complexes have been characterized by single-crystal X-ray structure determinations and solid-state 31P cross-polarization magic angle spinning (CP MAS) NMR spectroscopy. The salt [Ag(dppp-P,P)2]SCN is obtained as crystals suitable for X-ray studies from pyridine, crystallizing as a sesqui-pyridine solvate in the monoclinic space group P21/c with a = 10.691(2), b = 24.75(2), c = 22.360(4) , = 108.38(1)஠The neutral AgXP3 complexes (X = Cl, Br, I or CN) are isomorphous, crystallizing in the monoclinic space group C2/c, with a 21.8, b 10.3, c 45 , 95஠The solid-state 31P CP MAS spectra are consistent with the structural results; the tetrahedral SCN and NO3 complexes give a similar broad complex multiplet centred at -6, whereas the spectra of the neutral AgXP3 complexes are interpretable as A2BMX spin systems with signals assignable to the non-co-ordinated ( -23), bidentate ( ca. 13) and unidentate ( ca. 3) phosphorus atoms. For the latter 1J(P-Ag) couplings are in the range 288 Hz (CN) to 367 Hz (Br). Solution 31P NMR studies on these complexes show that both neutral and ionic complexes exist in equilibrium in solution, with the position of the equilibrium dependent on the nature of the anion X. The potential significance to the antitumour activity of bis-chelated 12 silver(I)-diphosphine complexes is discussed.