Observation of ligand effects during alkene hydrogenation catalysed by supported metal clusters

Abstract

Homogeneous organometallic catalysts and many enzymes activate reactants through coordination to metal atoms; that is, the reactants are turned into ligands and their reactivity controlled through other ligands in the metal's coordination sphere1. In the case of supported metal clusters, catalytic performance is influenced by the support and by adsorbed reactants, intermediates or products. The adsorbates are usually treated as ligands, whereas the influence of the supports is usually ascribed to electronic interactions2,3, even though metal clusters supported on oxides4,5,6 and zeolites7 form chemical bonds to support oxygen atoms. Here we report direct observations of the structure of supported metal clusters consisting of four iridium atoms, and the identification of hydrocarbon ligands bound to them during propene hydrogenation. We find that propene and molecular hydrogen form propylidyne and hydride ligands, respectively8, whereas simultaneous exposure of the reactants to the supported iridium cluster yields ligands that are reactive intermediates during the catalytic propane-formation reaction. These intermediates weaken the bonding within the tetrahedral iridium cluster and the interactions between the cluster and the support, while replacement of the MgO support with γ-Al2O3 boosts the catalytic activity tenfold, by affecting the bonding between the reactant-derived ligands and the cluster and therefore also the abundance of individual ligands. This interplay between the support and the reactant-derived ligands, whereby each influences the interaction of the metal cluster with the other, shows that the catalytic properties of supported metal catalysts can be tuned by careful choice of their supports.

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Figure 1: Infrared spectra of adsorbate ligands on Ir4/γ-Al2O3 during ethene hydrogenation.
Figure 2: Catalytic activity and average ethyl band intensity as a function of p H 2 during ethene hydrogenation catalysed by Ir4/γ-Al2O3.
Figure 3: Schematic representation of the hydrogenation of propene on MgO-supported Ir4.

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Acknowledgements

We thank the US National Science Foundation for support and the National Synchrotron Light Source at Brookhaven National Laboratory for beam time.

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Correspondence to B. C. Gates.

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Argo, A., Odzak, J., Lai, F. et al. Observation of ligand effects during alkene hydrogenation catalysed by supported metal clusters. Nature 415, 623–626 (2002). https://doi.org/10.1038/415623a

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