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Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles

Nature Chemistry volume 2, pages 36–41 (2010)Cite this article

Abstract

A continuing goal in catalysis is to unite the advantages of homogeneous and heterogeneous catalytic processes. To this end, nanoparticles represent a new frontier in heterogeneous catalysis, where this unification can also be supplemented by the ability to obtain new or divergent reactivity and selectivity. We report a novel method for applying heterogeneous catalysts to known homogeneous catalytic reactions through the design and synthesis of electrophilic platinum nanoparticles. These nanoparticles are selectively oxidized by the hypervalent iodine species PhICl2, and catalyse a range of π-bond activation reactions previously only catalysed through homogeneous processes. Multiple experimental methods are used to unambiguously verify the heterogeneity of the catalytic process. The discovery of treatments for nanoparticles that induce the desired homogeneous catalytic activity should lead to the further development of reactions previously inaccessible in heterogeneous catalysis. Furthermore, a size and capping agent study revealed that Pt PAMAM dendrimer-capped nanoparticles demonstrate superior activity and recyclability compared with larger, polymer-capped analogues.

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Figure 1: Depiction of the two nanoparticle synthesis techniques used and the initial reactivity results for electrophilic catalysis.
Figure 2: Monitoring the Pt nanoparticle catalysed reaction to show size and capping-agent effects as well as recyclability.
Figure 3: Cyclization reactions using Pt nanoparticles.
Figure 4: Cyclization reaction using Pd nanoparticles.
Figure 5: Oxidatively modified Pt nanoparticle catalysed cyclization of phenylurea 11.
Figure 6: Results from catalyst heterogeneity tests.

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Acknowledgements

We acknowledge support from the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geological and Biosciences of the US DOE under Contract DE-AC02-05CH11231.

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Authors and Affiliations

  1. Department of Chemistry, California 94720 and Chemical and Materials Sciences Divisions, University of California, Berkeley, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, 94720, California, USA

    Cole A. Witham, Wenyu Huang, Chia-Kuang Tsung, John N. Kuhn, Gabor A. Somorjai & F. Dean Toste

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  1. Cole A. Witham
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Contributions

C.A.W, W.H., C.-K.T. and J.N.K. performed the experiments and synthesized materials, substrates and catalysts. F.D.T. and G.A.S. supervised the research. All authors contributed to the conception of the experiments, discussed the results and commented on the manuscript.

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Correspondence to Gabor A. Somorjai or F. Dean Toste.

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Witham, C., Huang, W., Tsung, CK. et al. Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles. Nature Chem 2, 36–41 (2010). https://doi.org/10.1038/nchem.468

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