Insight in Structures of Superbulky Metallocenes with the CpBIG Ligand: Theoretical Considerations of Deca-Phenyl Metallocenes

Dennis Kuchenbecker (1) , Sjoerd Harder (1) , Georg Jansen (2)

1 The department of Chemistry
2 Fakultat fur Chemie

The structures of a series of deca-phenyl metallocenes (Ph5Cp)2M, which model superbulky metallocenes, are calculated by means of density functional theory including a semi-empirical correction for dispersion interactions (DFT+D). Through a detailed investigation of the calcocene it is shown that the interactions between the phenyl substituents of the two cyclopentadienyl ligands lead to a preference of S10-symmetrical structures and that dispersion interactions contribute to the overall stability of superbulky metallocenes. While the Ph substituents of the two ligands bend away from each other with standard DFT, inclusion of the dispersion correction reproduces the experimentally observed slight inclination towards each other. The experimentally observed linear correlation between the out-of-plane bending angle of the phenyl substituents and the size of the metal atom M (M = Fe, Ni, Cr, W, Ca, Yb, Sn, Sm, Sr, Ba) is also confirmed at the DFT+D level.

Mots clés: Physical Sciences

Dennis Kuchenbecker, Sjoerd Harder, Georg Jansen. Insight in Structures of Superbulky Metallocenes with the CpBIG Ligand: Theoretical Considerations of Deca-Phenyl Metallocenes. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, 2010, 636 (12), pp.2257. ⟨10.1002/zaac.201000192⟩. ⟨hal-00599874⟩