The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N2) remains a challenge because these molecules are often inert. The formation of carbon–nitrogen bonds from N2 typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N2 reactivity1, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N2 to form aniline derivatives. The key to this coupling reaction is the partial silylation of a reduced iron–dinitrogen complex, followed by migration of a benzene-derived aryl group to the nitrogen. Further reduction releases N2-derived aniline, and the resulting iron species can re-enter the cyclic pathway. Specifically, we show that an easily prepared diketiminate iron bromide complex2 mediates the one-pot conversion of several petroleum-derived arenes into the corresponding silylated aniline derivatives, by using a mixture of sodium powder, crown ether, trimethylsilyl bromide and N2 as the nitrogen source. Numerous compounds along the cyclic pathway are isolated and crystallographically characterized, and their reactivity supports a mechanism for sequential hydrocarbon activation and N2 functionalization. This strategy couples nitrogen atoms from N2 with abundant hydrocarbons, and maps a route towards future catalytic systems. An iron complex sequentially activates N2 and C–H bonds in benzene to form aniline, with coupling achieved through partial silylation of a reduced iron–nitrogen complex and phenyl migration.

中文翻译：

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通过芳基迁移偶联二氮和烃

碳氢化合物和大气中的氮 (N2) 等丰富分子的活化仍然是一个挑战，因为这些分子通常是惰性的。从 N2 形成碳氮键通常需要反应性有机前体，这些前体与促进 N2 反应性的还原条件不相容，从而阻止了催化作用。在这里，我们报告了一个二酮亚胺支持的铁系统，它依次激活苯和 N2 以形成苯胺衍生物。这种偶联反应的关键是还原铁-二氮络合物的部分硅烷化，然后苯衍生的芳基迁移到氮上。进一步还原会释放 N2 衍生的苯胺，由此产生的铁物质可以重新进入循环途径。具体来说，我们表明，通过使用钠粉、冠醚、三甲基甲硅烷基溴化物和 N2 的混合物作为氮源，易于制备的二酮亚胺溴化铁络合物 2 介导了几种石油衍生的芳烃向相应的甲硅烷基化苯胺衍生物的一锅法转化。沿着循环途径的许多化合物被分离出来并通过晶体学表征，它们的反应性支持了连续烃活化和 N2 功能化的机制。该策略将 N2 中的氮原子与丰富的碳氢化合物结合，并为未来的催化系统绘制了路线图。铁络合物依次激活苯中的 N2 和 C-H 键形成苯胺，通过还原铁氮络合物的部分硅烷化和苯基迁移实现偶联。