Valence Bond Approach of Metal−Ligand Bonding in the Dewar−Chatt−Duncanson ModelClick to copy article linkArticle link copied!
Abstract

Metal−ligand bonding, as considered in the Dewar−Chatt−Duncanson model, is described via an ab initio Valence Bond (VB) approach and applied to typical Pd−L complexes (L = NH3, PH3, CH2, SiH2). A progressive construction of the VB wave function is followed and leads to a very compact, though accurate, description of metal−ligand bonds. A description with the donation interaction only (ligand−metal) is first constructed and enriched so the back-donation interactions (metal−ligand) are also introduced. This latter VB wave function, although being extremely compact, provides bonding energies in agreement with standard (correlated) methods. A comparison between the two VB levels allows a quantification of adiabatic back-bonding energies and reveals very different trends between the ligands considered. A very faint back-donation in Pd−NH3 is found, which contrasts with a significant effect in Pd−PH3. Back-donation is, however, more important in Pd−XH2 complexes. In Pd−CH2, it is such that it even represents the major source of bonding. For Pd−SiH2, back-donation is slightly weaker than donation. The nature of the interaction in these metal−ligand complexes is revealed by the VB wave function analysis. Results are as well rationalized using the simple molecular orbital picture and compared to previous studies.
†
CNRS/Université Paul Cézanne (Aix-Marseille III).
*
To whom correspondence should be addressed. E-mail: braida@ lct.jussieu.fr (B.B.), [email protected] (S.H.).
‡
CNRS/Université Pierre et Marie Curie.
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