A Crystalline Singlet Phosphinonitrene: A Nitrogen Atom-Transfer Agent
A Crystalline Singlet Phosphinonitrene: A Nitrogen Atom-Transfer Agent
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DOI：
10.1126/science.1226022
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发表时间：
2012-09-21
期刊：
影响因子：
56.9
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Dielmann, Fabian;Back, Olivier;Bertrand, Guy
在模拟固氮酶生物固氮的中间体和工业上氮气的Haber-Bosch加氢制氨的背景下，分离和研究了各种过渡金属-硝基络合物(金属腈)。相比之下，非金属硝烯迄今只在低温下被光谱观察到，尽管它们在一系列有机反应中是中间体。在这里，我们报道了一种双(咪唑烷-2-亚胺)膦腈的合成，它在室温溶液中是稳定的，甚至可以在固体中分离出来。磷和氮之间的成键类似于观察到的金属腈的成键。我们还表明，这种氮磷衍生物可以用来将氮原子转移到有机碎片上，这对于过渡金属-硝基配合物来说是一项困难的任务。
A variety of transition metal-nitrido complexes (metallonitrenes) have been isolated and studied in the context of modeling intermediates in biological nitrogen fixation by the nitrogenase enzymes and the industrial Haber-Bosch hydrogenation of nitrogen gas into ammonia. In contrast, nonmetallic nitrenes have so far only been spectroscopically observed at low temperatures, despite their intermediacy in a range of organic reactions. Here, we report the synthesis of a bis(imidazolidin-2-iminato)phosphinonitrene, which is stable at room temperature in solution and can even be isolated in the solid state. The bonding between phosphorus and nitrogen is analogous to that observed for metallonitrenes. We also show that this nitrido phosphorus derivative can be used to transfer a nitrogen atom to organic fragments, a difficult task for transition metal-nitrido complexes.