Next Article in Journal
Immobilization/Stabilization of Ficin Extract on Glutaraldehyde-Activated Agarose Beads. Variables That Control the Final Stability and Activity in Protein Hydrolyses
Previous Article in Journal
Enhancing Light-Driven Production of Hydrogen Peroxide by Anchoring Au onto C3N4 Catalysts
Article Menu
Issue 4 (April) cover image

Export Article

Open AccessArticle
Catalysts 2018, 8(4), 148; https://doi.org/10.3390/catal8040148

Insights in the Rhodium-Catalyzed Tandem Isomerization-Hydroformylation of 10-Undecenitrile: Evidence for a Fast Isomerization Regime

1
Organometallics, Materials and Catalysis, UMR 6226 Institut des Sciences Chimiques de Rennes, CNRS-University of Rennes 1, F-35042 Rennes, France
2
Arkema France, CRRA, BP 63, Rue Henri Moissan, F-69493 Pierre Bénite, France
3
Arkema France, 420 Rue d’Estienne d’Orves, F-92705 Colombes, France
*
Author to whom correspondence should be addressed.
Received: 20 March 2018 / Revised: 27 March 2018 / Accepted: 2 April 2018 / Published: 5 April 2018
Full-Text   |   PDF [32410 KB, uploaded 3 May 2018]   |  

Abstract

The tandem isomerization-hydroformylation of 10-undecenitrile (1) into the corresponding linear aldehyde (2) with a Rh-biphephos system was studied and the formation of internal olefin isomers (1-int-x) was monitored over time. The existence of an “isomerization phenomenon” was evidenced, where fast isomerization of 1 into up to 70% of 1-int-x followed by fast back-isomerization of 1-int-x into 1 and, in turn, into 2 occurs. This fast dynamic isomerization regime is favored at high syngas pressure (40 bar) and low biphephos-to-Rh ratio (5–10), and it is best observed at relatively high catalyst loadings ([1]0/[Rh] ≤ 3000). The latter regime is indeed evanescent, and gives place to a second stage in which isomerization of internal olefins (and eventual conversion into 2) proceeds much more slowly. The results are tentatively rationalized by the formation of an unstable species that promotes dynamic isomerization and which slowly vanishes or collapses into a Rh-biphephos species which is the one responsible for hydroformylation. View Full-Text
Keywords: tandem reaction; hydroformylation; isomerization; rhodium; biphephos; undecenitrile tandem reaction; hydroformylation; isomerization; rhodium; biphephos; undecenitrile
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
SciFeed

Share & Cite This Article

MDPI and ACS Style

Le Goanvic, L.; Couturier, J.-L.; Dubois, J.-L.; Carpentier, J.-F. Insights in the Rhodium-Catalyzed Tandem Isomerization-Hydroformylation of 10-Undecenitrile: Evidence for a Fast Isomerization Regime. Catalysts 2018, 8, 148.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Catalysts EISSN 2073-4344 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top