Revisiting ultra-weak metal-metal bonding

Physical Review Letters, 1985

Computational and Theoretical Chemistry, 2019

Inorganic Chemistry, 2018

Molecules

About 70 years ago, in the framework of his theory of chemical bonding, Pauling proposed an empirical correlation between the bond valences (or effective bond orders (BOs)) and the bond lengths. Till now, this simple correlation, basic in the bond valence model (BVM), is widely used in crystal chemistry, but it was considered irrelevant for metal–metal bonds. An extensive analysis of the quantum chemistry data computed in the last years confirms very well the validity of Pauling’s correlation for both localized and delocalized interactions. This paper briefly summarizes advances in the application of the BVM for compounds with TM–TM bonds (TM = transition metal) and provides further convincing examples. In particular, the BVM model allows for very simple but precise calculations of the effective BOs of the TM–TM interactions. Based on the comparison between formal and effective BOs, we can easily describe steric and electrostatic effects. A possible influence of these effects on mat...

Journal of Physics and Chemistry of Solids, 1986

2011

Journal of The American Chemical Society, 1993

… , Computation, and Modeling (Theoretica Chimica Acta …, 2001

Angewandte Chemie International Edition, 2008