Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands.
Nat Chem. 2009 May;1(2):133-7. doi: 10.1038/nchem.167. Epub 2009 Apr 6.
Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.
均相催化反应可以通过激活潜伏催化剂来“开启”。通常,通过热或外部化学试剂来实现激活。然而,利用机械触发来激活均相催化剂尚未得到证明。在这里,我们介绍了一种通过机械打破金属与其配体之一之间的键来激活潜伏催化剂的通用方法。我们发现,聚合物功能化的 N-杂环卡宾的银(I)配合物是潜伏的有机催化剂,当在溶液中暴露于超声时,会催化酯交换反应。此外,带有附加聚合物链的钌双卡宾配合物的超声激活导致烯烃复分解反应的催化。在每种情况下,催化活性都源于配体的离解,这是由聚合物取代基向配位键传递机械力引起的。机械化学催化剂激活具有在机械信号的转导和放大中的潜在应用,并且机械引发的聚合有望成为自修复材料中的一种新型修复机制。