A Bidentate Ligand Featuring Ditopic Lewis Acids in the Second Sphere for Selective Substrate Capture and Activation.
A Bidentate Ligand Featuring Ditopic Lewis Acids in the Second Sphere for Selective Substrate Capture and Activation.
复制标题
一种二齿配体，在第二球体中具有二位路易斯酸，用于选择性底物捕获和激活。
DOI：
10.1002/anie.202218907
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Szymczak,NathanielK
中科院分区：
文献类型：
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作者：
Beagan,DanielM;Kiernicki,JohnJ;Zeller,Matthias;Szymczak,NathanielK
我们提出了一个以附加双位Lewis酸为特征的配体平台，以促进双原子底物的捕获/激活。我们发现，将两个9-硼双环[3.3.1]壬烷(9-BBN)单元结合到一个连接到吡啶吡唑支架上的单一碳上，保持了一组可用于配位FeII、ZnII和NiII的未淬灭的氮给体。利用氢化物离子亲和力和竞争实验，我们建立了与单位类似物相比，双位二次球状硼烷的加性效应。这些效应被用来在竞争阴离子如F-−和NO-3-−存在的情况下实现与NO_2-−的高选择性结合。最后，我们展示了肼在金属络合物的第二球体中的捕获，以及分别在锌和铁上生成肼和双氮烯配体的独特活化途径。
We present a ligand platform featuring appended ditopic Lewis acids to facilitate capture/activation of diatomic substrates. We show that incorporation of two 9‐borabicyclo[3.3.1]nonane (9‐BBN) units on a single carbon tethered to a pyridine pyrazole scaffold maintains a set of unquenched nitrogen donors available to coordinate FeII, ZnII, and NiII. Using hydride ion affinity and competition experiments, we establish an additive effect for ditopic secondary sphere boranes, compared to the monotopic analogue. These effects are exploited to achieve high selectivity for binding NO2−in the presence of competitive anions such as F−and NO3−. Finally, we demonstrate hydrazine capture within the second‐sphere of metal complexes, followed by unique activation pathways to generate hydrazido and diazene ligands on Zn and Fe, respectively.