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Homogeneous catalysis

On the trail of dioxygen activation

Nature volume 388, pages 332–333 (1997)Cite this article

An ‘ideal’ homogeneous catalyst for dioxygen (O2) oxidations would be selective, useful for tackling a variety of substrates and chemical structures, reasonably fast, and stable. Critically, and particular to the use of O2, the process should not require the wasteful addition of reducing agents. Such a system has remained a dream, but the work described by Neumann and Dahan on page 353of this issue1 constitutes notable progress towards realizing it.

All living matter and synthetic organic materials within the biosphere share a common condition and fate: they are thermodynamically unstable with respect to CO2 and H2O, products of reaction with O2. Fortunately for us, however, O2 is a diradical, possessing a triplet ground-state electronic configuration (two unpaired electrons), whereas almost everything else possesses singlet ground states (paired electrons only). Because of this difference in ground electronic states, strong electronic interactions, which go hand-in-hand with low activation barriers to chemical reactivity, are spinforbidden. This kinetic barrier is what makes the existence of life (as well as most synthetic organic materials) possible.

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Figure 1: The Neumann-Dahan1 catalyst, {[WZnRu2(OH)(H2O)](ZnW9O34.)2}11-, contains two sterically protected ruthenium atoms sandwiched between [ZnW9O34]12- halves (represented here as semicircles) of the oxidatively resistant polyoxometalate.

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Authors and Affiliations

  1. Department of Chemistry, Emory University, 1515 Pierce Drive, Atlanta, 30322, Georgia, USA

    Craig L. Hill & Ira A. Weinstock

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  1. Craig L. Hill
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  2. Ira A. Weinstock
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Hill, C., Weinstock, I. On the trail of dioxygen activation. Nature 388, 332–333 (1997). https://doi.org/10.1038/40986

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