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Beyond Ammonia: Nitrogen-Element Bond Forming Reactions with Coordinated Dinitrogen.
Chemical Reviews ( IF 62.1 ) Pub Date : 2020-05-27 , DOI: 10.1021/acs.chemrev.9b00705
Sangmin Kim 1 , Florian Loose 1 , Paul J Chirik 1
Affiliation  

The functionalization of coordinated dinitrogen to form nitrogen–element bonds en route to nitrogen-containing molecules is a long-standing challenge in chemical synthesis. The strong triple bond and the nonpolarity of the N2 molecule pose thermodynamic and kinetic challenges for promoting reactivity. While heterogeneous, homogeneous, and biological catalysts are all known for catalytic nitrogen fixation to ammonia, the catalytic synthesis of more complicated nitrogen-containing organic molecules has far less precedent. The example of silyl radical additions to coordinated nitrogen to form silylamines stands as the lone example of a catalytic reaction involving N2 to form a product other than ammonia. This Review surveys the field of molecular transition metal complexes as well as recent boron examples for the formation of nitrogen–element bonds. Emphasis is placed on the coordination and activation modes of N2 in the various metal compounds from across the transition series and how these structures can rationally inform reactivity studies. Over the past few decades, the field has evolved from the addition of carbon electrophiles in a manner similar to that of protonation reactions to more organometallic-inspired reactivity, including insertions, 1,2-additions, and cycloadditions. Various N–C, N–Si, and N–B bond-forming reactions have been discovered, highlighting that the challenge for catalytic chemistry is not in the reactivity of coordinated dinitrogen but rather removal of the functionalized ligand from the coordination sphere of the metal.

中文翻译:

超越氨:与协调的二氮形成氮元素键的反应。

在合成过程中,配位二氮官能化以形成含氮分子的氮元素键是一项长期的挑战。N 2分子的强三键和非极性构成了促进反应活性的热力学和动力学挑战。尽管均相,均相和生物催化剂均能将氮催化固氮成氨,但催化合成更复杂的含氮有机分子的先例却少得多。将甲硅烷基自由基加到配位氮中形成甲硅烷基胺的例子是涉及N 2的催化反应的唯一例子。形成氨以外的产物。这篇综述调查了分子过渡金属配合物的领域,以及最近关于形成氮元素键的硼实例。重点放在N 2的协调和激活方式上过渡系列中各种金属化合物的结构以及这些结构如何合理地指导反应性研究。在过去的几十年中,该领域已经从以类似于质子化反应的方式添加碳亲电试剂到更多的有机金属激发的反应性(包括插入,1,2-加成和环加成)演变。已经发现了各种N-C,N-Si和N-B键形成反应,这突出表明催化化学的挑战不是配位二氮的反应性,而是从金属配位域中除去官能化配体。
更新日期:2020-06-24
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