Predicting Dinitrogen Coupling with a Series of Small Molecules Catalyzed by a Pincer Complex |
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| Authors: | Qin Zhu Rulin Qiu Shicheng Dong Prof. Dr. Guixiang Zeng Prof. Dr. Jun Zhu |
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| Affiliation: | 1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Fujian Provincial Key Laboratory of Theoretical Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 P. R. China;2. Kuang Yaming Honors School, Institute for Brain Sciences, Nanjing University, Nanjing, 210093 P. R. China |
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| Abstract: | ![]()
Due to consumption of more than 2% of the world‘s annual energy supply by Haber–Bosch process and the strongest triple bond (N≡N) in nature, directly coupling N2 with small molecules is particularly important and challenging, let alone in a catalytic fashion. Here we first demonstrate that a NNN-type pincer phosphorus complex could act as a catalyst to couple dinitrogen with a series of small molecules including carbon dioxide, formaldehyde, N-ethylidenemethylamine, and acetonitrile in the presence of diborane(4) under a mild condition by theoretical calculations. N2 fixation proceeds via a stepwise mechanism involving initial N2 activation by diborane(4), followed by intramolecular isomerization to a key intermediate (zwitterion). Such a zwitterion can be used to couple a series of small molecules with activation barriers of 23.5–25.2 kcal mol−1. All these findings could be particularly useful for main group chemistry aimed at N2 activation. |
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| Keywords: | N2 Activation Pincer Complex Diborane(4) Small Molecule Activation DFT Calculation |
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