Issue 4, 2002

DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

Abstract

DFT(B3PW91) calculations of the activation of CH4 by models (Cl2LnZ) of Cp*2LnZ (Z = H, Me) have been carried out for the entire lanthanide series. Cl2LnZ appears to be a good model for Cp*2LnZ. It reproduces well the coordination around the lanthanide. The energetics of the transformation X2LnH + CH4 → X2LnCH3 + H2 are fairly close for X = Cl and Cp and the difference in behavior can be attributed to the stronger electron donating ability of Cp. Formation of the lanthanide hydride complex is calculated to be exothermic in agreement with experimental evidence. The energy profiles of the reactions Cl2LnH + CH4 → Cl2LnCH3 + H2; Cl2LnH* + CH4 → Cl2LnH + H*CH3; Cl2LnCH*3 + CH4 → Cl2LnCH3 + H–CH*3 have been calculated. The transition states for the first and third transformations are energetically accessible, in good agreement with the known experimental data. The second reaction has a transition state of very high energy indicating an unfeasible reaction. The geometry of the transition stuctures are suggestive of a proton transfer between two anionic species (Z and CH3; Z = H and CH3) in the field of the lanthanide fragment.

Graphical abstract: DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

Article information

Article type
Paper
Submitted
28 Aug 2001
Accepted
19 Dec 2001
First published
24 Jan 2002

J. Chem. Soc., Dalton Trans., 2002, 534-539

DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

L. Maron, L. Perrin and O. Eisenstein, J. Chem. Soc., Dalton Trans., 2002, 534 DOI: 10.1039/B107698C

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.

Spotlight

Advertisements