通过叠氮化物与阳离子二磷烯的环加成反应分离氮杂二磷杂环戊二烯和二磷杂环戊二烯。
Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene.
机构信息
Department of Chemistry and Food Chemistry, TU Dresden, Chair of Inorganic Molecular Chemistry, 01062, Dresden, Germany.
Department of Chemistry, Universitat de les Illes Balears, Palma de Mallorca, Spain.
出版信息
Angew Chem Int Ed Engl. 2017 May 22;56(22):6218-6222. doi: 10.1002/anie.201702058. Epub 2017 May 10.
The polarized, cationic diphosphene [( Im )P=P(Dipp)] as the triflate salt 7[OTf]( Im =4,5-dichloro-1,3-bis(Dipp)-imidazol-2-yl; Dipp=2,6-diisopropylphenyl) reacts with azides of type RN (R=Dipp or Dmp; Dmp=2,5-dimethylphenyl) in a [2+3] cycloaddition reaction followed by the release of N and a subsequent electrocyclic ring-closing reaction to azadiphosphiridine salts [( Im )P-P(Dipp)-N(R)]10a,b[OTf] (R=Dipp or Dmp). The reaction of 7[X] (X=OTf, GaCl ) with the electron-rich azides Me SiN and NaN give the unusual diphosphenimine derivatives [( Im )P-P(Dipp)=N(SiMe )] (11[OTf]) and [( Im )P-P(Dipp)=N(GaCl )] (12), respectively, featuring an acyclic P N moiety. Theoretical calculations provide insights into the reaction mechanisms to the cyclic and acyclic forms, in which the thermodynamic stability of the latter prevents the electrocyclic ring closure.
作为三氟甲磺酸盐 7[OTf]（Im=4,5-二氯-1,3-双（二异丙基苯基）-1H-咪唑-2-基；Dipp=2,6-二异丙基苯基）的极化阳离子二膦 [(Im)P=P(Dipp)]与 RN 型叠氮化物（R=Dipp 或 Dmp；Dmp=2,5-二甲基苯基）反应，在 [2+3]环加成反应后释放 N，并随后进行电环化闭环反应，得到氮杂二膦盐 [(Im)P-P(Dipp)-N(R)]10a,b[OTf]（R=Dipp 或 Dmp）。7[X]（X=OTf，GaCl）与富电子叠氮化物 MeSiN 和 NaN 的反应分别得到不寻常的二膦亚胺衍生物 [(Im)P-P(Dipp)=N(SiMe)]（11[OTf]）和 [(Im)P-P(Dipp)=N(GaCl)]（12），它们都具有非循环的 PN 部分。理论计算提供了对环状和非环状形式反应机制的深入了解，其中后者的热力学稳定性阻止了电环化闭环。
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