Frustrated Lewis Pairs
Frustrated Lewis Pairs
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DOI：
10.1021/jacs.5b06794
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发表时间：
2015-08-19
影响因子：
15
通讯作者：
Stephan, Douglas W.
中科院分区：
文献类型：
--
作者：
Stephan, Douglas W.
“受阻路易斯对”(FLP) 概念的阐述源于 H-2 可以通过空间阻碍的路易斯酸和碱的组合可逆激活的发现，这一发现引发了最近的大量活动。也许最显着的成果是用于一系列有机底物氢化的 FLP 催化剂的开发。在过去的 9 年里，底物范围已从庞大的极性物质发展到包括各种不饱和有机分子。此外，有效的立体选择性无金属加氢催化剂已经开始出现。人们已经探索了这种 H-2 活化的机制，并且能够实现这种活化的路易斯酸/碱组合的性质和范围也已经扩展到包括各种非金属物质。 FLP 与各种其他小分子（包括烯烃、炔烃和一系列元素氧化物）的反应性也已得到开发。尽管后一种化学反应已揭示了独特的化学计量转化，但无金属催化加氢胺化、二氧化碳还原化学以及在聚合中的应用也已实现。这一概念也开始在生物无机和材料化学以及多相催化中得到应用。本视角重点介绍了其中的许多进展，并讨论了 FLP 与已建立的化学之间的关系。还介绍了 FLP 化学未来可能出现的一些方向和发展。
The articulation of the notion of "frustrated Lewis pairs" (FLPs), which emerged from the discovery that H-2 can be reversibly activated by combinations of sterically encumbered Lewis acids and bases, has prompted a great deal of recent activity. Perhaps the most remarkable consequence has been the development of FLP catalysts for the hydrogenation of a range of organic substrates. In the past 9 years, the substrate scope has evolved from bulky polar species to include a wide range of unsaturated organic molecules. In addition, effective stereoselective metal-free hydrogenation catalysts have begun to emerge. The mechanism of this activation of H-2 has been explored, and the nature and range of Lewis acid/base combinations capable of effecting such activation have also expanded to include a variety of non-metal species. The reactivity of FLPs with a variety of other small molecules, including olefins, alkynes, and a range of element oxides, has also been developed. Although much of this latter chemistry has uncovered unique stoichiometric transformations, metal-free catalytic hydroamination, CO2 reduction chemistry, and applications in polymerization have also been achieved. The concept is also beginning to find applications in bioinorganic and materials chemistry as well as heterogeneous catalysis. This Perspective highlights many of these developments and discusses the relationship between FLPs and established chemistry. Some of the directions and developments that are likely to emerge from FLP chemistry in the future are also presented.