Structure and bonding in cyclic thiolate complexes of copper, silver and gold

The structures of Mn(SMe)n rings (M = Cu, Ag, Au; n = 2-6) and some of their PH3 and 1,4-diaza-1,3-butadiene complexes have been calculated using DFT methods. The geometries of the calculated structures are in good agreement with representative complexes retrieved from the Cambridge Crystallographic Data Base. Though π Cu–S and M–M orbital interactions can be identified, the net bonding interaction within the ring involves σ Cu–S orbital overlap. In many cases, the observed and calculated structures bear a similarity to those of appropriate members of the CnH2n series (n = 2–8).

Graphical abstractThe structure and bonding of cyclic thiolate complexes of copper, silver and gold has been examined by DFT calculationFigure optionsDownload full-size imageDownload as PowerPoint slide