Abstract
Homogeneous catalysts—which exist in the same (usually liquid) phase as reactants and products—are usually more selective than heterogeneous catalysts and far less affected by limitations due to slow transport of reactants and products, but their separation from reaction products can be costly and inefficient. This has stimulated the development of strategies that facilitate the recycling of homogeneous catalysts1,2,3,4. Some of these methods exploit the preference of a catalyst for one of two solvents with thermoregulated miscibility5,6; others exploit a dramatic decrease in catalyst solubility as one reagent is consumed7,8 or temperature changed after completion of the reaction9,10,11,12,13,14. Here we describe a tungsten catalyst for the solvent-free hydrosilylation of ketones that retains its activity until essentially all of the liquid substrate is converted to liquid products, which we can then simply decant to separate the catalyst that precipitates from the products of the reaction. We attribute the ability of the catalyst to retain its solubility and hence activity until completion of the reaction to the transient formation of liquid clathrate15,16 that contains a few molecules of the substrate per molecule of the otherwise solid catalyst. Insights into the fundamental processes controlling the formation of this liquid clathrate might help to tailor other catalysts and substrates, so as to develop efficient and solvent-free schemes for reactions of practical interest.
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This research was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, of the US Department of Energy.
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Dioumaev, V., Bullock, R. A recyclable catalyst that precipitates at the end of the reaction. Nature 424, 530–532 (2003). https://doi.org/10.1038/nature01856
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DOI: https://doi.org/10.1038/nature01856
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