Wydział Chemii

Juan Andrés

Sławomir Berski

M. Feliz

R. Llusar

F. Sensato

Bernard Silvi

2005

Comptes Rendus Chimie

8

1400-1412

10.1016/j.crci.2004.12.014

Naukowa

Angielski

Artykuł

The bonding in transition metal complexes is usually rationalized based on molecular orbital schemes. Topological approaches such as the atoms in molecules (AIM) theory or the electron localization function (ELF) analysis provides an alternative interpretation of the bonding relying on a local description. These topological theories give a very convenient framework to achieve the partition of the molecular space in regions with chemical meaning such as atoms, bonds and lone pairs. In this work we review the possibility offered by ELF to investigate the bond in di- tri- and tetranuclear metal complexes containing metal–metal bond. In the case of bimetallic complexes with different nominal bond orders of formula M₂(formamidinate)₄, the metal–metal interaction is associated to a large electron fluctuation between the two metallic cores and interpreted in terms of simple resonance arguments. Such fluctuation between metals can not be invoked for the trinuclear Fe₃(CO)₁₂ or the incomplete cuboidal [Mo₃S₄(PH₃)₆Cl₃]⁴⁺ complexes. The metal–metal interaction in these clusters is mostly characterized by multicenter bonding as is the case for the tetranuclear heterodimetallic cubane-type complexes resulting from the insertion of Cu or Ni into the previous Mo₃S₄ complex.

http://dx.doi.org/10.1016/j.crci.2004.12.014

http://www.elsevier.com