The structural definition of adducts of stoichiometry MX:dppx (1:1) M = CuI, AgI, X = simple anion, dppx=Ph2P(CH2)xPPh2, x = 3–6

Single crystal X-ray structural characterizations are recorded for a wide range of adducts of the form MX:dppx (1:1)(n), M = silver(I) (predominantly), copper(I), X = simple (pseudo-) halide or oxy-anion (the latter spanning, where accessible, perchlorate, nitrate, carboxylate – a range of increasing basicity), dppx=bis(diphenylphosphino)alkane, Ph2P(CH2)xPPh2, x = 3–6. Adducts are defined of two binuclear forms: (i) [LM(μ-X)2L], with each ligand chelating a single metal atom, and (ii) [M(μ-X)2(μ-(P-L-P′))2M′] where both ligands L and halides bridge the two metal atoms; a few adducts are defined as polymers, the ligands connecting M(μ-X)2M′ kernels, this motif persisting in all forms. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR).