Bent Phosphaallenes With "Hidden" Lone Pairs as Ligands
Bent Phosphaallenes With "Hidden" Lone Pairs as Ligands
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以“隐藏”孤对电子作为配体的弯曲磷杂烯
DOI：
10.1002/chem.201900645
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发表时间：
2019-06-12
影响因子：
4.3
通讯作者：
Grutzmacher，Hansjorg
中科院分区：
文献类型：
--
作者：
Chen，Xiaodan;Li，Zhongshu;Grutzmacher，Hansjorg
磷杂烯R−P=C=L, L = N -杂环碳烯（NHCs），在一定程度上可以看作是被NHCs稳定的磷异腈，R−P=C：←L。研究了这些分子作为金属离子配体的适宜性，并在大多数情况下通过中心碳中心观察到配位。实验、光谱方法和DFT计算的结合表明，在R−P=C：←L的碳中心存在一个隐藏电子对。值得注意的是，这对孤对也插入到分子内的C−H键中，显示出磷异腈预期的碳型反应性。
Phosphaheteroallenes R−P=C=L, with L = N‐heterocyclic carbenes (NHCs), can be viewed to a certain extent as phosphaisonitriles stabilized with NHCs, R−P=C:←L. The suitability of these molecules as ligands for coinage‐metal ions was investigated and coordination through the central carbon center was observed in most cases. A combination of experiments, spectroscopic methods, and DFT calculations indicates the presence of a hidden electron pair at the carbon center of R−P=C:←L. Remarkably, this lone pair also inserts intramolecularly in C−H bonds showing the carbene‐type reactivity which is expected for phosphaisonitriles.