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Activation of a Metal-Halogen Bond by Halogen Bonding.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-05-30 , DOI: 10.1002/anie.202005214
Julian Wolf 1 , Florian Huber 2 , Nikita Erochok 1 , Flemming Heinen 1 , Vincent Guérin 3 , Claude Y Legault 3 , Stefan F Kirsch 2 , Stefan M Huber 1
Affiliation  

In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal‐ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal‐halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives were shown to be effective activators in two test reactions and their activity could be modulated by blocking of the Lewis acidic sites. Bis(benzimidazolium)‐based halogen bonding activators provided even more rapid conversion, while the non‐iodinated reference compound showed little activity. The role of halogen bonding in the activation of metal‐halogen bonds was further investigated by NMR experiments and DFT calculations, which support the mode of activation occurring via halogen bonding.

中文翻译:

通过卤素键激活金属-卤素键。

近年来,卤素键(XB)的非共价相互作用在有机催化中的应用日益广泛。但是,迄今为止,有关XB激活金属配体键的报道仅限于与元素碘或溴发生的少数反应。本文中,我们介绍了两类惰性卤素键供体对金属-卤素键的活化作用,以及在均相金催化中使用所得活化配合物。在两个测试反应中,仅有的最近探索的一类碘鎓衍生物被证明是有效的活化剂,它们的活性可以通过封闭路易斯酸性位点来调节。基于双(苯并咪唑鎓)的卤素键活化剂可提供更快的转化率,而未碘化的参比化合物则几乎没有活性。
更新日期:2020-05-30
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