Jump to main content
Jump to site search

Issue 10, 2004
Previous Article Next Article

Modelling Me5C5 for reactivity studies in (η5-C5Me5)2Ln–R: full DFT and QM/MM approaches

Author affiliations

Abstract

DFT (B3PW91) and QM/MM (ONIOM) calculations have been carried out to compare several models of the cyclopentadienyl ligand (L) for the insertion of ethylene into the Ln–C bond of L2Ln–Et and β-H transfer to the incoming monomer. Calculations have been carried out for C5Me5 (Cp*) where all atoms are explicitly treated at the DFT level, for C5Me5 (Cp#) at the QM/MM (B3PW91:UFF) level where the Me groups are taken into account by a molecular force field, C5H5 (Cp) and Cl. Comparisons of these systems provide information about the stereoelectronic effects of the ligands on the elementary steps of the reaction. Although Cp# has the steric properties of Cp* but the electronic properties of Cp, the geometry and energy barriers are very close for Cp* and Cp# suggesting that steric effects outweigh the electronic effects of the Me groups of the cyclopentadienyl ligand.

Graphical abstract: Modelling Me5C5 for reactivity studies in (η5-C5Me5)2Ln–R: full DFT and QM/MM approaches

Back to tab navigation

Publication details

The article was received on 24 Mar 2004, accepted on 11 May 2004 and first published on 16 Sep 2004


Article type: Paper
DOI: 10.1039/B404478A
Citation: New J. Chem., 2004,28, 1255-1259
  •   Request permissions

    Modelling Me5C5 for reactivity studies in (η5-C5Me5)2Ln–R: full DFT and QM/MM approaches

    L. Perrin, L. Maron and O. Eisenstein, New J. Chem., 2004, 28, 1255
    DOI: 10.1039/B404478A

Search articles by author

Spotlight

Advertisements