Distiboranes based on ortho -phenylene backbones as bidentate Lewis acids for fluoride anion chelation
Distiboranes based on ortho -phenylene backbones as bidentate Lewis acids for fluoride anion chelation
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基于邻亚苯基主链的二硼烷作为二齿路易斯酸用于氟阴离子螯合
DOI：
10.1039/d1ob00536g
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发表时间：
2021
影响因子：
3.2
通讯作者：
Gabbaï, François P.
中科院分区：
文献类型：
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作者：
You, Di;Zhou, Benyu;Hirai, Masato;Gabbaï, François P.
作为我们在支持阴离子传感和传输的主基团平台化学方面的努力的一部分，我们现在报告以 o-C6F4 主链为特色的基于锑的二齿路易斯酸的合成。这些化合物可以通过新合成的 o-C6F4(SbPh2)2 (5) 与邻四氯苯醌或八氟菲-9,10-醌反应轻松获得，得到相应的通式 o-C6F4(SbPh2(二醇))2 的二硼烷 6 和 7，其中二醇=四氯儿茶酚（6）和八氟菲-9,10-二醇（7），分别。虽然 6 的溶解度非常差，但其八氟菲-9,10-二醇类似物 7 很容易溶解在 CH2Cl2 中，并迅速转化为相应的氟化物螯合物 [7-μ2-F]−，该络合物已作为 [nBu4N]+ 盐分离出来。 7的o-C6H4类似物，称为8，也已制备。虽然路易斯酸性比 7 低，但 8 也形成非常稳定的氟化物螯合物 ([8-μ2-F]−)。总而言之，我们的实验结果，加上计算分析和氟化物阴离子亲和力计算，表明 7 和 8 是迄今为止制备的最强的锑基氟化物阴离子螯合剂。这项工作的另一个值得注意的方面涉及八氟菲-9,10-二醇配体的使用及其赋予有利的溶解度和路易斯酸性性质的能力。
As part of our efforts in the chemistry of main group platforms that support anion sensing and transport, we are now reporting the synthesis of anitmony-based bidentate Lewis acids featuring the o-C6F4 backbone. These compounds can be easily accessed by reaction of the newly synthesized o-C6F4(SbPh2)2 (5) with o-chloranil or octafluorophenanthra-9,10-quinone, affording the corresponding distiboranes 6 and 7 of general formula o-C6F4(SbPh2(diolate))2 with diolate = tetrachlorocatecholate for 6 and octafluorophenanthrene-9,10-diolate for 7, respectively. While 6 is very poorly soluble, its octafluorophenanthrene-9,10-diolate analog 7 readily dissolves in CH2Cl2 and undergoes swift conversion into the corresponding fluoride chelate complex [7-μ2-F]− which has been isolated as a [nBu4N]+ salt. The o-C6H4 analog of 7, referred to as 8, has also been prepared. Although less Lewis acidic than 7, 8 also forms a very stable fluoride chelate complex ([8-μ2-F]−). Altogether, our experiental results, coupled with computational analyses and fluoride anion affinity calculations, show that 7 and 8 are some of the strongest antimony-based fluoride anion chelators prepared to date. Another notable aspect of this work concerns the use of the octafluorophenanthrene-9,10-diolate ligand and its ablity to impart advantageous solubility and Lewis acidity properties.