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Understanding and exploiting C–H bond activation

Nature volume 417, pages 507–514 (2002)Cite this article

Abstract

The selective transformation of ubiquitous but inert C–H bonds to other functional groups has far-reaching practical implications, ranging from more efficient strategies for fine chemical synthesis to the replacement of current petrochemical feedstocks by less expensive and more readily available alkanes. The past twenty years have seen many examples of C–H bond activation at transition-metal centres, often under remarkably mild conditions and with high selectivity. Although profitable practical applications have not yet been developed, our understanding of how these organometallic reactions occur, and what their inherent advantages and limitations for practical alkane conversion are, has progressed considerably. In fact, the recent development of promising catalytic systems highlights the potential of organometallic chemistry for useful C–H bond activation strategies that will ultimately allow us to exploit Earth's alkane resources more efficiently and cleanly.

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Figure 1: An example of agostic bonding.
Figure 2: Possible structures of sigma complexes.
Figure 3: Pathway for oxidative addition of an alkane.
Figure 4: Detailed mechanism of oxidative addition.
Figure 5: Mechanism of methane oxidation in the Shilov system48.
Figure 6: Hypothetical sequence for alkane oxidation to alcohol by O2 and catalysed by a Pt(II) complex.
Figure 7: The Catalytica system for methane oxidation58.

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  1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California, 91125, USA

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Labinger, J., Bercaw, J. Understanding and exploiting C–H bond activation. Nature 417, 507–514 (2002). https://doi.org/10.1038/417507a

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