Silver(I) complexes with the mixed P/O donor ligand Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2 (L-1) and the crystal structures of [Ag(L-1)](CF3SO3), [Ag-2(L-1)(3)](CF3SO3)(2) and [Ag(L-1)(NO3)]

The Ag(l) salts AgY (Y = ClO4, CF3SO3, NO3, Cl or I) react with one molar e quivalent of the diphosphinodiether ligand Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PP h2 (L-1) to give 1:1 species of stoichiometry Ag(L-1)Y. The structures of t hese species have been investigated in solution by P-31 NMR spectroscopy an d for [Ag(L-1)](ClO4), [Ag(L-1)](CF3SO3) and [Ag(L-1)(NO3)] in the solid st ate by single crystal X-ray diffraction. In particular, the Ag-107-P and Ag -109-P coupling constants provide a convenient method for identifying the s olution speciation, especially for the occurrence of anion coordination in the nitrate and halide complexes. The conclusions from the NMR spectroscopi c studies are also consistent with the solid state structures. Addition of a further equivalent of L-1 to [Ag(L-1)](CF3SO3) results in a very signific ant drop in the Ag-P coupling constants, indicative of higher P-coordinatio n at Ag(l), now involving three P-donor atoms. This conclusion is also born e out by a crystallographic study on [Ag-2(L-1)(3)](CF3SO3)(2) which shows a dinuclear cation with one chelating L-1 and one bridging L-1 ligand coord inated to each metal centre, giving a distorted trigonal planar geometry. ( C) 2001 Elsevier Science Ltd. All rights reserved.