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Mapping boron catalysis onto a phosphorus cluster platform
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-11-17 , DOI: 10.1039/d2dt03657f
Benjamin L L Réant 1 , Bono van IJzendoorn 1 , George F S Whitehead 2 , Meera Mehta 1
Affiliation  

Clusters of main group elements, such as phosphorus, arsenic, germanium, and tin – called Zintl clusters – have been known for more than a century. However, their application in main group catalysis is largely unknown. Here, we tether boranes to a seven-atom phosphorus cluster ({C8H14}BCH2CH2SiMe2)3P7 (2) and we demonstrate Lewis acid catalysis as proof-of-principle that boron chemistry can be mapped onto clusters using this method. Catalyst 2 was employed to mediate key organic transformations, including the hydroboration of carbodiimides, isocyanates, ketones, alkenes, alkynes, and nitriles. To the best of our knowledge, this is the first application of Zintl-based clusters as an innocent platform in metal-free catalysis. By chaining boron, its treasure chest of chemistry can be unlocked at these clusters. Hence, beyond catalysis this method could find applications for main group clusters in neutron capture therapy, stimuli responsive materials, and cross-coupling, and frustrated Lewis pair and functional polymer chemistries.

中文翻译:

将硼催化映射到磷簇平台上

磷、砷、锗和锡等主族元素的簇——称为 Zintl 簇——已经为人所知一个多世纪了。然而,它们在主基团催化中的应用在很大程度上是未知的。在这里,我们将硼烷束缚在一个七原子磷簇 ({C 8 H 14 }BCH 2 CH 2 SiMe 2 ) 3 P 7 ( 2 ) 上,并且我们展示了路易斯酸催化作为可以绘制硼化学的原理证明使用此方法到群集上。催化剂2被用来介导关键的有机转化,包括碳二亚胺、异氰酸酯、酮、烯烃、炔烃和腈的硼氢化反应。据我们所知,这是基于 Zintl 的团簇作为无金属催化中的无害平台的首次应用。通过链接硼,可以在这些簇中解锁它的化学宝库。因此,除了催化作用之外,该方法还可以在中子俘获疗法、刺激响应材料、交叉耦合以及受挫路易斯对和功能聚合物化学中找到主族团簇的应用。
更新日期:2022-11-17
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