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

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.