This work was partly supported by a French–German PROCOPE contract (no. 94132). Calculations were carried out on the IBM RS 6000 workstations of our laboratory and of the Institut du Developpement et de Ressources en Informatique Scientifique (IDRIS, Orsay), and on the DEC 3000/600S workstations of the Centre Universitaire Régional de Ressources Informatiques (CURRI, Strasbourg). We thank the staff of these two centers for their cooperation. We are also grateful to Dr. L. Padel and Mrs. Fersing for their help and technical assistance.
σ Metathesis as a Critical Step for the Transition Metal Catalyzed Formation of Formic Acid from CO2 and H2? An Ab Initio Investigation†
Article first published online: 22 DEC 2003
Copyright © 1995 by VCH Verlagsgesellschaft mbH, Germany
Angewandte Chemie International Edition in English
Volume 34, Issue 16, pages 1742–1745, September 1, 1995
How to Cite
Hutschka, F., Dedieu, A. and Leitner, W. (1995), σ Metathesis as a Critical Step for the Transition Metal Catalyzed Formation of Formic Acid from CO2 and H2? An Ab Initio Investigation. Angew. Chem. Int. Ed. Engl., 34: 1742–1745. doi: 10.1002/anie.199517421
- Issue published online: 22 DEC 2003
- Article first published online: 22 DEC 2003
- Manuscript Revised: 13 MAY 1995
- Manuscript Received: 17 MAR 1995
- ab initio calculations;
- carbon dioxide;
- rhodium compounds
The hydrogenation of CO2 to formic acid catalyzed by three-coordinate d8 hydridorhodium complexes has been studied by ab initio calculations on [HRh(PH3)2] as the model catalyst. A catalytic cycle involving a 2σ + 2σ metathesis reaction between H2 and [Rh(PH3)2(O2CH)], in which rhodium remains in the oxidation state I, is proposed as an alternative to the traditional pathway involving RhI/RhIII oxidation/reduction sequences.