One-, Two-, and Three-Electron Reduction of a Cyclic Alkyl-(amino)carbene-SbCl3 Adduct
One-, Two-, and Three-Electron Reduction of a Cyclic Alkyl-(amino)carbene-SbCl3 Adduct
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DOI：
10.1002/anie.201404849
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发表时间：
2014-07-28
影响因子：
16.6
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Kretschmer, Robert;Ruiz, David A.;Bertrand, Guy
环烷基(氨基)卡宾很容易与SbCl3反应生成相应的Sb-III加合物。单电子还原产生了第一个以溶液为特征的以锑为中心的中性自由基。两电子还原得到Lewis碱稳定的二氯二苯乙烯，而三电子还原得到由两个卡宾封端的Sb双原子物种。用EPR谱对其结构进行了表征，用单晶X-射线衍射法确定了其他三种化合物的结构。在这四个物种中，类金属的形式氧化态从III到II，再到I，最后是0。
A cyclic alkyl(amino)carbene readily reacts with SbCl3 to form the corresponding Sb-III adduct. One-electron reduction gives rise to the first example of a neutral antimony-centered radical characterized in solution. Two-electron reduction affords a Lewis base stabilized chloro-stibinidene, whereas three-electron reduction gives an antimony diatomic species capped by two carbenes. The radical has been characterized by EPR spectroscopy, while the structure of the other three species has been ascertained by single-crystal X-ray diffraction. In these four species, the formal oxidation state of the metalloid diminishes from III, to II, to I, and finally 0.