Vladimir K. Dioumaev

A recyclable catalyst that precipitates at the end of the reaction

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 catalysts. Some of these methods exploit the preference of a catalyst for one of two solvents with thermoregulated miscibility; others exploit a dramatic decrease in catalyst solubility as one reagent is consumed or temperature changed after completion of the reaction. 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 clathrate 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.

An N-heterocyclic carbene as a bidentate hemilabile ligand: a synchrotron X-ray diffraction and density functional theory studyElectronic supplementary information (ESI) available: experimental details and characterization data; table of results for hydrogenation of 3-pentanone; Gaussian 98 summary for the W and Mo models; ORTEP plot of 1W and crystal data. See http://www.rsc.org/suppdata/cc/b3/b303762b/

The N-heterocyclic carbene ligand IMes was shown by synchrotron crystallography and DFT computations to adopt a hemilabile bidentate coordination mode in CpM(CO)2(IMes)+B(C6F5)4− n(M = Mo, W), with a CC bond of one mesityl weakly coordinated to the metal.