Scandium-Promoted Direct Conversion of Dinitrogen into Hydrazine Derivatives via N–C Bond Formation,Journal of the American Chemical Society

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Scandium-Promoted Direct Conversion of Dinitrogen into Hydrazine Derivatives via N–C Bond Formation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-05-22 , DOI: 10.1021/jacs.9b04293
Ze-Jie Lv ₁ , Zhe Huang ₁ , Wen-Xiong Zhang ₁ , Zhenfeng Xi ₁

Affiliation

Direct conversion of dinitrogen (N2) into organic compounds, not through ammonia (NH3), is of great significance both fundamentally and practically. Here we report a highly efficient scandium-mediated synthetic cycle affording hydrazine derivatives (RMeN-NMeR') directly from N2 and carbon-based electrophiles. The cycle includes three main steps: (i) reduction of a halogen-bridged discandium complex under N2 leading to a (N2)3--bridged discandium complex via a (N2)2- intermediate; (ii) treatment of the (N2)3- complex with methyl triflate (MeOTf), affording a (N2Me2)2--bridged discandium complex; and (iii) further reaction of the (N2Me2)2- complex with the carbon-based electrophile, producing the hydrazine derivative and regenerating the halide precursor. Furthermore, insertion of a CO molecule into one Sc-N bond in the (N2Me2)2--scandium complex was observed. Most notably, this is the first example of rare-earth metal-promoted direct conversion of N2 to organic compounds; the formation of C-N bonds by the reaction of these (N2)3- and (N2Me2)2- complexes with electrophiles represents the first case among all N2-metal complexes reported.

中文翻译：

钪通过 N-C 键形成促进二氮直接转化为肼衍生物

将二氮 (N2) 直接转化为有机化合物，而不是通过氨 (NH3)，从根本上和实践上都具有重要意义。在这里，我们报告了一种高效的钪介导的合成循环，可直接从 N2 和碳基亲电试剂中提供肼衍生物 (RMeN-NMeR')。该循环包括三个主要步骤： (i) 在 N2 下还原卤素桥连的二钪络合物，通过 (N2)2- 中间体生成 (N2)3--桥连的二钪络合物；(ii) 用三氟甲磺酸甲酯 (MeOTf) 处理 (N2)3- 络合物，得到 (N2Me2)2--桥接的二氧化钛络合物；(iii) (N2Me2)2-配合物与碳基亲电试剂的进一步反应，产生肼衍生物并再生卤化物前体。此外，观察到 CO 分子插入到 (N2Me2)2-钪络合物中的一个 Sc-N 键中。最值得注意的是，这是稀土金属促进 N2 直接转化为有机化合物的第一个例子；这些 (N2)3- 和 (N2Me2)2- 配合物与亲电子试剂反应形成 CN 键是所有 N2-金属配合物报道的首例。

更新日期：2019-05-22

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