Abstract
The following silver(I) complexes ofN-ethylthiourea, L, have been isolated in the solid state: AgLX (X = Cl, Br, ClO4, BF4, and CF3CO2), Ag2L3X2 (X=ClO4, BF4 and CF3CO2), AgL2ClO4, AgL3X (X = Cl, Br, I, ClO4, BF4 and CF3CO2). The decrease of theν(CS) and σ(SCN2) frequencies in the i.r. spectra of the complexes indicates S-coordination of the ligands. Theν(AgS) frequencies lie in the 267–252 cm−1 range for terminal and 240-210 cm−1 range for bridged or “long” Ag-S bonds. The following structures may be proposed for the complexes. AgLX (X = Cl and Br), polymeric trigonal coordination with bridging halide ions; Ag2L3A2 (A = ClO4 and BF4), polymeric trigonal coordination with three bridging sulphur atoms; AgL2ClO4, polymeric tetrahedral coordination with four bridging sulphur atoms; AgL3A (A = ClO4 and BF4), dimeric tetrahedral coordination with two terminal and two bridging sulphur atoms; AgLO2CCF3 and Ag2L3(O2CCF3)2, trigonal and/or tetrahedral coordination with terminal sulphur bonds and bridging CO2 groups; AgL3O2CCF3, tetrahedral coordination with terminal sulphur bonds and a monodentate CO2 group. In the trifluoroacetato complexes, aν(AgO) band is observed at 185–209 cm−1. The AgL3X complexes (X = Cl, Br and I) show twoν(AgX) and twoν(AgS) bands with rather low frequencies corresponding to “long” metal-ligand bond distances.
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