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Catalysis in service of main group chemistry offers a versatile approach to p-block molecules and materials

Nature Chemistry volume 5, pages 817–829 (2013)Cite this article

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Abstract

Catalytic reactions that enable the formation of new bonds to carbon centres play a pervasive role in the state-of-the-art synthesis of organic molecules and macromolecules. In contrast, the development of analogous processes as routes to main group compounds and materials has been much slower. Nevertheless, recent advances have led to a broad expansion of this field and now allow access to a wide range of catenated structures based on elements across the p block. These breakthroughs have already impacted areas such as hydrogen storage and transfer, functional inorganic polymers and ceramic thin films. Dehydrogenation and dehydrocoupling processes are particularly well developed and may be mediated by either transition metal or main group catalysts. Such pathways represent an increasingly attractive and convenient alternative to traditional routes, such as salt metathesis and reductive coupling reactions. An overview of this emerging area is presented in this Review with a focus on recent developments and future challenges.

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Figure 1: Early examples of catalytic dehydrocoupling to form homonuclear (E–E) and heteronuclear (E–E′) bonds.
Figure 2: E–H bond comparisons and periodic trends for p-block main group elements.
Figure 3: Synthetic routes to homonuclear and heteronuclear lighter main group element–element bonds.
Figure 4: Potential applications for dehydrocoupling processes involving adducts of groups 13–15.
Figure 5: Synthetic routes for the formation of homonuclear heavier main group bonds.
Figure 6: Developing mechanistic insight for the catalytic formation of group 14 polymers.
Figure 7: A summary of representative catalysts and relevant catalytic cycles for the dehydrogenation and dehydrocoupling of adducts of groups 13–15 to form oligomeric and polymeric N–B and P–B species.
Figure 8: Recent breakthroughs in catalytic dehydrocoupling and other coupling processes for p-block elements.

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Acknowledgements

The authors acknowledge financial support from the Engineering and Physical Sciences Research Council. E.M.L. and T.J. thank the Marie Curie International Incoming Fellowship for funding. G. R. Whittell (Univ. Bristol, UK) is acknowledged for comments and discussion.

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  1. Erin M. Leitao and Titel Jurca: These authors contributed equally to this work

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  1. School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK

    Erin M. Leitao, Titel Jurca & Ian Manners

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Leitao, E., Jurca, T. & Manners, I. Catalysis in service of main group chemistry offers a versatile approach to p-block molecules and materials. Nature Chem 5, 817–829 (2013). https://doi.org/10.1038/nchem.1749

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