Issue 10, 2004

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

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

Article information

Article type
Paper
Submitted
24 Mar 2004
Accepted
11 May 2004
First published
16 Sep 2004

New J. Chem., 2004,28, 1255-1259

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements