The structural definition of adducts of stoichiometry AgX:dppf (1:1)(n), X = simple anion, dppf = bis(diphenylphosphino)ferrocene

Single crystal X-ray structural characterizations are recorded for an array of adducts of the form AgX:dppf (1:1)(n), X = simple (pseudo-)halide or oxy-anion, ‘dppf’ = bis(diphenyl phosphino)ferrocene, for adducts X = Cl (new phase), Br, I, SCN, OCN, CN, NO3 (new phase), O2CCH3, n = 2, the form being dimeric [(dppf-P,P′)Ag(μ-X)2Ag(P,P′-dppf)], for X = I, SCN, [Ag(μ-X)2(P-dppf-P′)2Ag′]; for X = O2CCF3, n = ∞, the form is an extended polymer: ⋯Ag(O · CO · CF3)(P-dppf-P′)Ag′(O⋯. A dichloromethane solvate phase of CuI:dppf (1:1)2 (also centrosymmetric) is also recorded. 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). The topology of the structures in the solid state was found to depend on the nature of the counterion.