A Singlet Phosphinidene Stable at Room Temperature
A Singlet Phosphinidene Stable at Room Temperature
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DOI：
10.1016/j.chempr.2016.04.001
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发表时间：
2016-07-07
期刊：
影响因子：
23.5
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Liu, Liu;Ruiz, David A.;Bertrand, Guy
我们报道了一种碳烯的磷类似物的合成，即磷二烯，在室温下固态稳定数周。该化合物为（膦）膦烯，是通过辐照诱导从相应的（膦）磷烯中去除一氧化碳而制备的。由于取代基的电子性质，该化合物具有PP多键，类似于稳定的单线态氨基羰基，具有氮碳双键。它与缺电子的烯烃发生[2 + 1]环加成反应，与异腈发生[1 + 1]偶联反应。我们还发现，在没有空间位保护的情况下，单线态膦烯二聚形成相应的二膦烯。
We report the synthesis of a phosphorus analog of carbenes, namely a phosphinidene, that is stable for weeks in the solid state at room temperature. This compound, a (phosphino) phosphinidene, was prepared by irradiation-induced elimination of carbon monoxide from the corresponding (phosphino) phosphaketene. Because of the electronic properties of the substituent, this compound features a PP multiple bond, similarly to stable singlet aminocarbenes, which feature a nitrogen-carbon double bond. It undergoes a [2 + 1] cycloaddition with an electron-poor alkene and a [1 + 1] coupling reaction with isonitriles. We also show that, without steric protection, singlet phosphinidenes dimerize to give the corresponding diphosphenes.