Metal-Free σ-Bond Metathesis in Ammonia Activation by a Diazadiphosphapentalene
Metal-Free σ-Bond Metathesis in Ammonia Activation by a Diazadiphosphapentalene
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DOI：
10.1021/ja509963m
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发表时间：
2014-12-03
影响因子：
15
通讯作者：
Kinjo, Rei
中科院分区：
文献类型：
--
作者：
Cui, Jingjing;Li, Yongxin;Kinjo, Rei
合成了桥头带有两个磷原子的具有弯曲构型的二氮杂磷杂环戊烯衍生物5。在温和的条件下，化合物5容易活化氨，得到含烯胺基的1-氮杂-2，3-二膦烯衍生物6。因此，该反应被认为是氨的N-H键和5的内环P-N键之间的正式S键易位反应。通过密度泛函理论计算，探讨了氨活化和随后的异构化的反应机理。
A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal s-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.