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The role of the milling environment on the copper-catalysed mechanochemical synthesis of tolbutamideUnder controlled atmospheres the mechanochemical synthesis of tolbutamide is catalysed by Cu(ii), with CuCl acting as a pre-catalyst, activatedviaaerobic oxidation under milling. Use of aluminum jars results in mechanoinhibition of this process.more » « less
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Using the mechanosynthesis of the calcium urea phosphate fertilizer cocrystal as a model, we provide a quantitative investigation of chemical autocatalysis in a mechanochemical reaction. The application of in situ Raman spectroscopy and synchrotron X-ray powder diffraction to monitor the reaction of urea phosphate and either calcium hydroxide or carbonate enabled the first quantitative and in situ study of a mechanochemical system in which one of the products of a chemical reaction (water) mediates the rate of transformation and underpins positive feedback kinetics. The herein observed autocatalysis by water generated in the reaction enables reaction acceleration at amounts that are up to 3 orders of magnitude smaller than in a typical liquid-assisted mechanochemical reaction.more » « less
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Mechanochemistry reveals a novel polymorph of the mercury(II) imidazolate framework, based on square-grid (sql) topology layers. Reaction monitoring and periodic density functional theory calculations show that the sql-structure is of higher stability than the previously reported three-dimensional framework, with the unexpected stabilization of the lower dimensionality structure arising from weak interactions that include short interlayer C-H···Hg contacts, highlighting a potential role for agostic interactions in directing metal-organic framework topology.more » « less
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