TY - JOUR
T1 - Influence of Relativistic Effects on Bonding Modes in M(II) Dinuclear Complexes (M = Au, Ag, and Cu)
AU - Jerabek, Paul
AU - Von Der Esch, Beatriz
AU - Schmidbaur, Hubert
AU - Schwerdtfeger, Peter
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/12/4
Y1 - 2017/12/4
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85037638049&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.7b02434
DO - 10.1021/acs.inorgchem.7b02434
M3 - Article
C2 - 29135228
AN - SCOPUS:85037638049
SN - 0020-1669
VL - 56
SP - 14624
EP - 14631
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -