The reductive coupling of dinitrogen
The reductive coupling of dinitrogen
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DOI：
10.1126/science.aav9593
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发表时间：
2019-03-22
期刊：
影响因子：
56.9
通讯作者：
Braunschweig, Holger
中科院分区：
文献类型：
--
作者：
Legare, Marc-Andre;Rang, Maximilian;Braunschweig, Holger
两个或多个二氮分子（N-2）的耦合在电离层中的辐射条件下自然发生，并且可以在超高压或等离子体条件下合成实现。然而，相对较低的N-N单键焓通常使得强三键N-2双原子的正链化不利，氮链的分解是常见的反应基序。在这里，我们报道了令人惊讶的有机硼介导的两个N-2分子在近环境条件下形成一个配合物，其中[N-4]（2-）链桥接两个硼中心。该反应需要在一个步骤中还原耦合两个低价硼结合的N-2单位。该配合物和链两端质子化的衍生物都进行了晶体学表征。
The coupling of two or more molecules of dinitrogen (N-2) occurs naturally under the radiative conditions present in the ionosphere and may be achieved synthetically under ultrahigh pressure or plasma conditions. However, the comparatively low N-N single-bond enthalpy generally renders the catenation of the strongly triple-bonded N-2 diatomic unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, we report the surprising organoboron-mediated catenation of two N-2 molecules under near-ambient conditions to form a complex in which a [N-4](2-) chain bridges two boron centers. The reaction entails reductive coupling of two hypovalent-boron-bound N-2 units in a single step. Both this complex and a derivative protonated at both ends of the chain were characterized crystallographically.