화학공학소재연구정보센터
Inorganic Chemistry, Vol.56, No.23, 14624-14631, 2017
Influence of Relativistic Effects on Bonding Modes in M(II) Dinuclear Complexes (M = Au, Ag, and Cu)
The stability and bonding in dinuclear group 11 metal complexes (M = Au, Ag, and Cu) in their +2 oxidation state has been investigated by quantum chemical methods. Two model complexes were selected as representatives of different bonding situations in the dinuclear M(II) complexes, a direct metal-metal bond between two ligand stabilized monomers and ligand-mediated bridged dimer system, making them interesting for a direct comparison and to study the influence of relativistic effects. Relativity substantially stabilizes the direct metal metal bonded system obtaining the sequence in M-M bond stability Au > Ag > Cu. In the ligand-bridged structure, an asymmetric bonding situation is obtained for gold, resulting in two stronger/covalent and two weaker/ionic bonds per gold atom. Here we observe the opposite trend in stability Cu > Ag > Au. Our analysis nicely corroborates with what is known from experimental observation.