Journal
ORGANOMETALLICS
Volume 27, Issue 22, Pages 5852-5859Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om800420r
Keywords
-
Categories
Funding
- DSM Pharmaceuticals
- Ministere de l'Enseignement Superieur et de la Recherche (France)
- Centre National pour la Recherche Scientifique (France)
Ask authors/readers for more resources
The mechanism of asymmetric hydrogen transfer catalyzed by a ruthenacycle has been studied. Ruthenium-hydride intermediates have been characterized by H-1 NMR and IR. These hydride complexes appeared as a diastereomeric mixture (de = 64%) responsible for the enantiomeric excess of the hydrogen transfer reaction (ee = 60%). Kinetic measurements have been performed as a function of substrate concentration and temperature. Michaelis-Menten kinetics were observed indicating substrate-catalyst complex formation (thermodynamic data for the complexation reaction: Delta G(0) = -13 kJ mol(-1) at 273 K, Delta H-0 = -58 kJ mol(-1), Delta S-0 = -170 J K-1 mol(-1)). The complexation process is accomplished prior to an intracomplex chemical reaction. As the substrate is still bound to the catalyst, pericyclic hydrogen transfer is deduced with an activation energy E-a = 83 kJ mol(-1). On the basis of these data, a mechanism is proposed for the overall hydrogen transfer reaction.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available