Metal-Free Bond Activation by Carboranyl Diphosphines
Metal-Free Bond Activation by Carboranyl Diphosphines
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DOI：
10.1021/jacs.1c05387
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发表时间：
2021-07-13
影响因子：
15
通讯作者：
Peryshkov, Dmitry, V
中科院分区：
文献类型：
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作者：
Gange, Gayathri B.;Humphries, Amanda L.;Peryshkov, Dmitry, V
我们报告了碳硼烷双膦1-（PBu 2）-Bu-t-2-（PPr 2）-Pr-i-C2 B10 H10的无金属键活化。该主族元素系统包含碱性结合位点，并具有通过两电子氧化还原态循环的能力。所报道的与选定的主基团C1-C4和醇的反应通过膦基团的形式氧化和伴随的硼笼的还原而发生。这些转换，这是由电子给体外取代基和电子接受集群之间的合作驱动，不同于那些“常规”膦，并让人想起氧化除了过渡金属中心，从而代表了一种新的方法，无金属键活化。
We report metal-free bond activation by the carboranyl diphosphine 1-(PBu2)-Bu-t-2-(PPr2)-Pr-i-C2B10H10. This main group element system contains basic binding sites and possesses the ability to cycle through two-electron redox states. The reported reactions with selected main group hydrides and alcohols occur via the formal oxidation of the phosphine groups and concomitant reduction of the boron cage. These transformations, which are driven by the cooperation between the electron-donating exohedral substituents and the electron-accepting cluster, differ from those of "regular" phosphines and are reminiscent of oxidative addition to transition metal centers, thus representing a new approach to metal-free bond activation.