English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Effect of Ligand Electronics on the Reversible Catalytic Hydrogenation of CO2 to Formic Acid Using Ruthenium Polyhydride Complexes: A Thermodynamic and Kinetic Study

MPS-Authors
/persons/resource/persons132873

Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons255530

Schubert,  Lukas
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons237767

Bordet,  Alexis
Research Department Leitner, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons58749

Leitner,  Walter
Research Department Leitner, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Institut für Technische Chemie und Makromolekulare Chemie, Rheinisch‐Westfälische Technische Hochschule Aachen, Worringer Weg 1, 52074 Aachen, Germany;

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Estes, D. P., Leutzsch, M., Schubert, L., Bordet, A., & Leitner, W. (2020). Effect of Ligand Electronics on the Reversible Catalytic Hydrogenation of CO2 to Formic Acid Using Ruthenium Polyhydride Complexes: A Thermodynamic and Kinetic Study. ACS Catalysis, 10(5), 2990-2998. doi:10.1021/acscatal.0c00404.


Cite as: http://hdl.handle.net/21.11116/0000-0007-A6E2-E
Abstract
Hydrogenation of CO2 to formic acid or formates is often carried out using catalysts of the type H4Ru(PR3)(3) (1). These catalysts are also active for the reverse reaction, i.e., the decomposition of formic acid to H-2 and CO2. While numerous catalysts have been synthesized for reactions in both directions, the factors controlling the elementary steps of the catalytic cycle remain poorly understood. In this work, we synthesize a series of compounds of type H4Ru(P(C6H4R)(3))(3) containing both electron-donating and electron-withdrawing groups and analyze their influence on the kinetic and thermodynamic parameters of CO2 insertion and deinsertion. The data are correlated with the catalytic performance of the complexes through linear free-energy relationships. The results show that formic acid dissociation from the catalyst is rate-determining during CO2 hydrogenation, while deinsertion is critical for the decomposition reaction.