Dong Shicheng, Zhu Jun
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, Guangdong 518172, China.
Inorg Chem. 2024 Aug 26;63(34):15984-15992. doi: 10.1021/acs.inorgchem.4c02391. Epub 2024 Aug 14.
Although main group species have emerged in the field of dinitrogen activation in recent years, the reported examples are particularly rare in comparison with transition metal complexes due to their significant challenges. Herein, we demonstrate a [4 + 2] cycloaddition reaction of N (with an activation energy as low as 12.5 kcal mol) initiated by an inorganic benzene via density functional theory calculations. Such N activation is supported by the elongated nitrogen-nitrogen bond distance (), decreased vibration frequency (ν), and weakened Wiberg bond index (WBI). Subsequently, the "push-pull" electronic effect, formed by introducing a Lewis acid, HB(CF), facilitates the generation of thermodynamically more stable products. In addition, this inorganic benzene could also be used to activate a series of small molecules, including carbon dioxide, acetylene, ethylene, and acetonitrile with reaction barriers ranging from 4.7 to 11.6 kcal mol. Our findings provide an alternative approach to N activation and functionalization, theoretically validating the feasibility of the dual Lewis acid strategy for dinitrogen activation.
尽管近年来主族物种已出现在二氮活化领域，但由于存在重大挑战，与过渡金属配合物相比，已报道的例子特别稀少。在此，我们通过密度泛函理论计算证明了由无机苯引发的N的[4 + 2]环加成反应（活化能低至12.5 kcal/mol）。这种N活化得到了氮 - 氮键长延长（）、振动频率降低（ν）和维伯格键指数（WBI）减弱的支持。随后，通过引入路易斯酸HB(CF)形成的“推 - 拉”电子效应促进了热力学上更稳定产物的生成。此外，这种无机苯还可用于活化一系列小分子，包括二氧化碳、乙炔、乙烯和乙腈，反应势垒范围为4.7至11.6 kcal/mol。我们的研究结果为N活化和功能化提供了一种替代方法，从理论上验证了二氮活化双路易斯酸策略的可行性。
