Structural and electronic analysis of lanthanide complexes : the nature of the lanthanide atom may be not necessarily innocent towards reactivity – a DFT study

Sandra Schinzel (1) , Martin Bindl (1) , Marc Visseaux (2) , Henry Chermette (1)

1 LC - Laboratoire de Chimie - UMR5182
2 UCCS - Unité de Catalyse et Chimie du Solide - UMR 8181

Density functional theory (DFT) calculations were used to study a given complex for the whole series of lanthanide cations: [Ln(C3H5)Cp(OMe)] (1) [Ln = La (Z = 57) - Lu (Z = 71)], the radioactive lanthanide promethium (Z = 61) excepted. Contrarily to the common assumptions, the calculations suggest a significant, albeit indirect, contribution of f electrons to bonding. Relativistic effects were considered in the calculations of the bonding energies, as well as in geometry optimisations in both spin-restricted and unrestricted formalisms. The unrestricted orbitals have finally been used for the analysis of the charges and the composition of the frontier orbitals. It is confirmed that the ionic character is more pronounced for complexes of the late lanthanides.

Mots clés: lanthanide; rare earth; complexes; catalysis; electronic structure; theory

Domaines: Chimie théorique et/ou physique; Chimie de coordination

Sandra Schinzel, Martin Bindl, Marc Visseaux, Henry Chermette. Structural and electronic analysis of lanthanide complexes : the nature of the lanthanide atom may be not necessarily innocent towards reactivity – a DFT study. Journal of Physical Chemistry A, 2006, 110, pp.11324-11331. ⟨10.1021/jp060876d⟩. ⟨hal-00105916⟩