Use of thio and seleno germanones as ligands: silver(I) halide complexes with Ge═E→Ag-I (E = S, Se) moieties and chalcogen-dependent argentophilic interaction

Abstract

The potential of thio and seleno germanones [LPhGe═E] (L = aminotroponiminate (ATI) ligand, E = S 3, Se 4) to function as ligands has been demonstrated through the isolation of their silver(I) iodide complexes [{(t-Bu)2ATIGe(E)Ph}2(Ag2I2)] (E = S 5, Se 6) with a planar and discrete Ag2I2 core. Compounds 5 and 6 possess the hitherto unknown Ge═E→Ag-I moieties and the crystallographic data reveals the presence of a strong argentophilic interaction (2.950(1) Å) in complex 6, but is inconclusive in complex 5 (3.470(1) Å). Using theoretical studies, proof for the presence and absence of argentophilic interactions in complexes 6 and 5 was obtained, respectively. Further, it is disclosed that the donor ability of the chalcogen atoms in the Ge═E→Ag-I moieties dictate the Ag···Ag interaction in these complexes.