Elusive Antimony-Centered Radical Cations: Isolation, Characterization, Crystal Structures, and Reactivity Studies
Elusive Antimony-Centered Radical Cations: Isolation, Characterization, Crystal Structures, and Reactivity Studies
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难以捉摸的锑中心自由基阳离子：分离、表征、晶体结构和反应性研究
DOI：
10.1002/anie.201610334
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发表时间：
2017-01-09
影响因子：
16.6
通讯作者：
Wang, Xinping
中科院分区：
文献类型：
--
作者：
Li, Tao;Wei, Houjia;Wang, Xinping
锑化合物芳基（3）Sb的单电子氧化（1）Aryl= 2，6-iPr（2）-4-OMe-C6H2; 2，芳基= 2，4，6-Pr-1（3）-C6 H2）与AgSbF 6和NaB芳基（4）（F）（芳基（F）= 3，5-（CF 3）（2）C6 H3）得到了第一个结构表征的锑中心自由基阳离子1的实例（中心点+）[B λ ryl（4）（F）]（-）和2（中心点+）[B λ ryl（4）（F）]（-）。用电子晶体X射线衍射、电子顺磁共振谱（EPR）和紫外/维斯吸收光谱研究了它们的分子结构和电子结构，并结合理论计算进行了分析.此外，它们的反应性进行了研究。2（中心点+）[BAryl（4）（F）]（-）与对苯醌反应，合成了双核锑二价盐3（2+）[BAryl（4）（F）]（2）（-），并对其进行了NMR和X射线衍射分析。二价阳离子3（2+）的形成进一步证实了孤立的锑化氢自由基阳离子是以锑为中心的。
One-electron oxidation of the stibines Aryl(3)Sb (1, Aryl=2,6-iPr(2)-4-OMe-C6H2; 2, Aryl=2,4,6-Pr-i(3)-C6H2) with AgSbF6 and NaBAryl(4)(F) (Aryl(F) = 3,5-(CF3)(2)C6H3) afforded the first structurally characterized examples of antimony-centered radical cations 1(center dot+)[B Lambda ryl(4)(F)](-) and 2(center dot+)[B Lambda ryl(4)(F)](-). Their molecular and electronic structures were investigated by singlecrystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/ Vis absorption spectroscopy, in conjunction with theoretical calculations. Moreover, their reactivity was investigated. The reaction of 2(center dot+)[BAryl(4)(F)](-) and p-benzoquinone afforded a dinuclear antimony dication salt 3(2+)[BAryl(4)(F)](2)(-), which was characterized by NMR spectroscopy and X-ray diffraction analysis. The formation of the dication 3(2+) further confirms that the isolated stibine radical cations are antimony-centered.