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Issue 31, 2019
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Effector responsive hydroformylation catalysis

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Abstract

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

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Supplementary files

Article information


Submitted
26 May 2019
Accepted
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

Chem. Sci., 2019,10, 7389-7398
Article type
Edge Article

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

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