Issue 31, 2019

Effector responsive hydroformylation catalysis


Herein, we report a supramolecular rhodium complex that can form dimeric or monomeric Rh-species catalytically active in hydroformylation, depending on the binding of effectors within the integrated DIM-receptor. X-ray crystal structures, in situ (high-pressure (HP)) spectroscopy studies, and molecular modelling studies show that in the absence of effectors, the preferred Rh-species formed is the dimer, of which two ligands coordinate to two rhodium metals. Importantly, upon binding guest molecules, -effectors-, to the DIM-receptor under hydroformylation conditions, the monomeric Rh-active species is formed, as evidenced by a combination of in situ HP NMR and IR spectroscopy studies and molecular modelling. As the monomeric complex has different catalytic properties from the dimeric complex, we effectively generate a catalytic system of which the properties respond to the presence of effectors, reminiscent of how the properties of proteins are regulated in nature. Indeed, catalytic and kinetic experiments show that both the selectivity and activity of this supramolecular catalytic system can be influenced in the hydroformylation of 1-octene using acetate as an effector that shift the equilibrium from the dimeric to monomeric species.

Graphical abstract: Effector responsive hydroformylation catalysis

Supplementary files

Article information

Article type
Edge Article
26 May 2019
15 Jun 2019
First published
19 Jun 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 7389-7398

Effector responsive hydroformylation catalysis

S. Bai, V. Sinha, A. M. Kluwer, P. R. Linnebank, Z. Abiri, P. Dydio, M. Lutz, B. de Bruin and J. N. H. Reek, Chem. Sci., 2019, 10, 7389 DOI: 10.1039/C9SC02558H

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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.

Social activity