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of styrenes, at least in the case of catalysis with unsupported
clusters.
Despite the remarkable stability of Au25(SR)18 nanoclusters,
questions remain regarding their viability as homogeneous
catalysts.14 The nature of the true catalytic species is an impor-
tant consideration in reaction development, especially within
the realm of atomically defined nanoclusters.34,44 While these
species have immense potential owing to their aforementioned
stability and unique electronic properties, that potential can only
be fully realized by exploiting reactions wherein the clusters
themselves are likely to survive.
Herein we have presented evidence that not only are Au25(SR)18
clusters unstable to oxidations with TBHP, but also that the Au–thiol
cluster precursor and cluster decomposition products are equally
effective in the oxidation of styrene. Even at temperatures signifi-
cantly lower than that of the reaction, TBHP completely decomposes
Au25(SR)18 before notable product appearance is observed. Further,
kinetic poisoning experiments have shown that far more than one
equivalent of poison per gold atom is required to observe any
meaningful reduction in reaction rate – indicating that the active
catalytic species is likely not the intact cluster. Lastly, XPS studies
show that the Au species present after decomposition and before
cluster formation are Au(I), which indicates that Au(I) thiolates are
likely the active catalyst in this reaction.
¨
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The authors would like to acknowledge M. A. Tofanelli and
E. D. Jackson for their assistance in gathering XPS data.
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Chem. Commun.
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