The structural definition of adducts of stoichiometry MX:dpex (2:3)(∞), M = CuI, AgI, X =simple anion, dpex = Ph2E(CH2)xEPh2, 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)(x)EPh2 (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)(2)AsPh2), X = Br, F3CCO2 (= 'tfa'), F3CSO3 ( 'tfs'), dpex = 'dpape' (Ph2As(CH2)(2)PPh2), X = CN, SCN, OClO3) are one-dimensional polymers mers center dot center dot center dot -E')(1)AgX(E-dpex-E')(2)-AgX(E-dpex-E')(1)AgX center dot center dot center dot, P, As sites scrambled in the latter. AgNO3:dpam (2:3) is also a one-dimensional polymer, center dot center dot center dot AgO center dot NO center dot OAg(As-dpam-As)AgO center dot NO center dot OAg center dot center dot center dot ('dpam' Ph2As(CH2)(2)AsPh2). 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)(2)AsPh2)(3)] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (H-1, (31)p NMR, ESI MS) and in the solid state (IR). (c) 2005 Elsevier B.V. All rights reserved.