The structural definition of adducts of stoichiometry MX : dpex (2 : 3)((infinity)), M = Cu-I, Ag-I, X =simple anion, dpex = Ph2E(CH2)(x)EPh2, E = P, As

Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph2E(CH2)xEPh2 (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe-P,P′)CuX(P-dppe-P′)CuX(P,P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph2As(CH2)2AsPh2), X = Br, F3CCO2 (= ‘tfa’), F3CSO3 (≡ ‘tfs’); dpex = ‘dpape’ (Ph2As(CH2)2PPh2), X = CN, SCN, OClO3) are one-dimensional polymers ⋯–E′)1AgX(E-dpex-E′)2-AgX(E-dpex-E′)1AgX⋯, P, As sites scrambled in the latter. AgNO3:dpam (2:3) is also a one-dimensional polymer, ⋯AgO·NO·OAg(As-dpam-As)AgO·NO·OAg⋯ (‘dpam’ ≡ Ph2As(CH2)2AsPh2). AgX:dpae (2:3) (X = I, CN, ClO4, NO3) and AgX:dpape (2:3) (X = Br, I, NO3) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph2P(CH2)2AsPh2)3] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (1H, 31P NMR, ESI MS) and in the solid state (IR).