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

Abstract

Single-crystal X-ray structural characterizations of MX:dpam (1:1) (‘dpam’ = Ph 2AsCH 2AsPh 2) 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’ = Ph 2As(CH 2) 2AsPh 2, 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).