New oligo-/poly-meric forms for MX:dpex (1:1) complexes (M = Cu I, AgI; X = (pseudo-)halide; dpex = Ph 2E(CH2)xEPh2, E = (P), As; X = 1, 2)

Article abstract of DOI:10.1016/j.ica.2004.07.026

Single-crystal X-ray structural characterizations of MX:dpam (1:1) ('dpam' = Ph₂AsCH₂AsPh₂) are reported for MX = AgCl, Br; CuI, CN/Cl (all isomorphous) and AgI, AgSCN, CuSCN arrays, all being of the novel form [(μ-X){M(μ-X)(As-dpam-As′)₂M′}] _∞, essentially the familiar M(E-dpem-E′) ₂M′ binuclear array with both 'bridging' and (linking) 'terminal' (pseudo-)halides involved in the polymer. A different arrangement of bridging and linking entities is found with AgX:dpae (1:1) _2(∞|∞), X = Br, NCO, 'dpae' = Ph₂As(CH ₂)₂AsPh₂, now comprising [M(μ-X) ₂(As-dpae-As)M] kernels linked by As-dpae-As′, while in the thiocyanate analogue Ag(_NCS^SCN)Ag units are linked by the dpae ligands into a two-dimensional web. 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).