Adatom mediated adsorption of N-heterocyclic carbenes on Cu(111) and Au(111)

The adsorption of N-heterocyclic carbenes (NHCs) on Cu(111) and Au(111) surfaces is studied with density-functional theory. The role of the molecular side groups as well as the surface morphology in determining the adsorption geometry are explored in detail. Flat-laying NHCs, as observed experimentally for NHC with relatively small side groups, result from the adsorption at adatoms and give rise to the so-called ballbot configurations, which are more stable than adsorption on flat surfaces and provide an efficient precursor for the formation of bis(NHC) dimers. On Au(111), the resulting (NHC)₂ Au complexes are purely physisorbed and thus mobile. On the more reactive Cu(111), in contrast, the central Cu atom in the (NHC)₂ Cu dimer is still covalently bound to the surface, resulting in a mobility, which has to be thermally activated.