State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, P. R. China.
Chem Asian J. 2021 Jun 14;16(12):1626-1633. doi: 10.1002/asia.202100394. Epub 2021 May 21.
As the strongest triple bond in nature, the N≡N triple bond activation has always been a challenging project in chemistry. On the other hand, since the award of the Nobel Prize in Chemistry in 1950, the Diels-Alder reaction has served as a powerful and widely applied tool in the synthesis of natural products and new materials. However, the application of the Diels-Alder reaction to dinitrogen activation remains less developed. Here we first demonstrate that a transition-metal-involved [4+2] Diels-Alder cycloaddition reaction could be used to activate dinitrogen without an additional reductant by density functional theory calculations. Further study reveals that such a dinitrogen activation by 1-metalla-1,3-dienes screened out from a series of transition metal complexes (38 species) according to the effects of metal center, ligand, and substituents can become favorable both thermodynamically (with an exergonicity of 28.2 kcal mol ) and kinetically (with an activation energy as low as 13.8 kcal mol ). Our findings highlight an important application of the Diels-Alder reaction in dinitrogen activation, inviting experimental chemists' verification.
作为自然界中最强的三键，N≡N 三键的活化一直是化学中的一个具有挑战性的课题。另一方面，自 1950 年诺贝尔化学奖设立以来，Diels-Alder 反应已成为合成天然产物和新材料的有力且广泛应用的工具。然而，Diels-Alder 反应在氮气活化方面的应用仍然不够发达。在这里，我们首次通过密度泛函理论计算证明，通过过渡金属参与的[4+2] Diels-Alder 环加成反应，可以在没有额外还原剂的情况下激活氮气。进一步的研究表明，根据金属中心、配体和取代基的影响，从一系列过渡金属配合物（38 种）中筛选出的 1-金属-1,3-二烯可以使这种氮气活化在热力学上（具有 28.2 kcal/mol 的放热性）和动力学上（具有低至 13.8 kcal/mol 的活化能）都变得有利。我们的发现突出了 Diels-Alder 反应在氮气活化中的一个重要应用，邀请实验化学家进行验证。
