(L)2C2P2: Dicarbondiphosphide Stabilized by N-Heterocyclic Carbenes or Cyclic Diamido Carbenes
(L)2C2P2: Dicarbondiphosphide Stabilized by N-Heterocyclic Carbenes or Cyclic Diamido Carbenes
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(L)(2)C2P2：由 N-杂环卡宾或环状二酰氨基卡宾稳定的二碳二磷化物
DOI：
10.1002/anie.201612247
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发表时间：
2017-05-15
影响因子：
16.6
通讯作者：
Grutzmacher, Hansjorg
中科院分区：
文献类型：
--
作者：
Li, Zhongshu;Chen, Xiaodan;Grutzmacher, Hansjorg
碳磷化物（CnPm）可能具有非常有前途的电子、光学和机械性能，但它们在实验上几乎是未开发的材料。由n -杂环碳烯稳定的磷杂烯经过单电子还原得到结构多样的(L)(2)C2P2型化合物。以咪唑烷基为配体的L得到中心有四元环C2P2的配合物，而亲电性更强的环二胺羰基（DAC）则得到具有无环偶联CP-PC单元的配合物。环状C2P2化合物最好描述为非kekul 8分子，它们通过与NHC配体NHC ->(C2P2)-> NHC配位而稳定。这些物质很容易被氧化生成稳定的自由基[(NHC)(2)C2P2]（+中心点）。用电子共享键(DAC)=C=P-P=C=(DAC)来描述具有丙烯酸C2P2核的非常稳定的分子。
Carbon phosphides, CnPm, may have highly promising electronic, optical, and mechanical properties, but they are experimentally almost unexplored materials. Phosphaheteroallenes stabilized by N-heterocyclic carbenes undergo a one-electron reduction to yield compounds of the type (L)(2)C2P2 with diverse structures. The use of imidazolylidenes as ligands L give complexes with a central four-membered ring C2P2, while more electrophilic cyclic diamidocarbenes (DAC) give a compound with an acyclic pi-conjugated CP-PC unit. Cyclic C2P2 compounds are best described as non-Kekul 8 molecules that are stabilized by coordination to the NHC ligands NHC ->(C2P2)-> NHC. These species can be easily oxidized to give stable radical cations [(NHC)(2)C2P2](+center dot). The remarkably stable molecules with an acylic C2P2 core are best described with electron-sharing bonds (DAC)=C=P-P=C=(DAC).