Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis
Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis
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DOI：
10.1039/c0sc00533a
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发表时间：
2011-01-01
期刊：
影响因子：
8.4
通讯作者：
Sanders, Jeremy K. M.
中科院分区：
文献类型：
--
作者：
Belenguer, Ana M.;Friscic, Tomislav;Sanders, Jeremy K. M.
我们证明了在共价机械合成的可逆性和热力学控制，通过使用碱催化的芳族二硫化物的复分解反应作为模型反应。机械力化学形成的热力学平衡的混合物，观察净和液体辅助研磨方法。不同的方法导致相互不同的平衡组成，这也不同于通过溶液平衡获得的那些。这些差异可以解释为晶体堆积效应叠加在孤立分子的固有反应性上。计算表明，反应物和产物在其各自的晶体结构中的相对能量的差异可以使机械化学反应平衡偏向于反应物完全转化为产物，从而为固态动态组合合成的发展和使用机械化学的固态合成的合理设计打开了大门。
We demonstrate the reversibility and thermodynamic control in covalent mechanosynthesis, by using the base-catalysed metathesis of aromatic disulfides as a model reaction. The mechanochemical formation of thermodynamic equilibrium mixtures is observed for both neat and liquid-assisted grinding methodologies. Different methodologies lead to mutually different equilibrium compositions, which also differ from those obtained by solution equilibration. The differences can be explained in terms of crystal packing effects superimposed onto the inherent reactivity of isolated molecules. Calculations indicate that the differences in relative energies of reactants and products in their respective crystal structures can bias the mechanochemical reaction equilibrium towards the complete conversion of reactants into the product, in that way opening the doors for the development of dynamic combinatorial synthesis in the solid state and for the rational design of solid-state synthesis using mechanochemistry.