Recently, Ma Jiabi, associate professor of North Institute of chemistry and chemical engineering, conducted an in-depth study on the reactivity and structure of N₂and CO₂with aunbbo − gas-phase clusters through the combination of mass spectrometry experiment and theoretical chemical calculation, and realized the direct coupling of N₂and CO₂to form two N − C bonds at room temperature, and follow a new N₂activation mode, metal ligand activation (MLA), which we proposed earlier. The relevant achievements are entitled "room temperature dinitrogen and carbon dioxide activation to form nitrogen − carbon bonds by Quaternary cluster anions: Gold assisted enhancement of reactivity", Published in the international authoritative journal the Journal of Physical Chemistry Letters (2022, 13, 492 − 497). Ding Yongqi, a doctoral student of the school of chemistry and chemical engineering, is the first author, and Ma Jiabi, a teacher of our school, is the corresponding author of the paper.

N₂and CO₂are very inert small molecules. It is very challenging to activate and couple N₂and CO₂under mild conditions to directly form N − C bonds and convert them into valuable chemical products. In 2019, the team found that Ta₃N₃H⁻and Ta₃N₃⁻clusters with active sites of 2 and 3 Ta atoms can completely activate N₂molecules and generate adsorption products Ta₃N₅H⁻and Ta₃N5⁻(J. Am. Chem. Soc. 2019, 141, 12592-12600). On this basis, in 2021, the team proposed the metal ligand activation (MLA) model, realized the reaction of directly coupling N2 and CO2 molecules by NbH₂⁻clusters at room temperature, and realized the preparation of C−N bonds from N₂and CO₂(J. Phys. Chem. Lett. 2021, 12, 3490-3496). In the same year, the team found that the single metal anion NbB₃O₂⁻cluster can efficiently convert N₂to two nitrogen-containing productsB₃N₂O⁻/NbO and B₃N₂O₂⁻/Nb at room temperature, and further realize the catalytic cycle of the reaction (J. Phys. Chem. Lett. 2021, 12, 6313-6319).

Fig. 1 Sequential reaction diagram of AuNbBO− Anion Cluster with N₂and CO₂

With the support of the major research plan of NSFC, Ma Jiabi, associate professor of the school of chemistry and chemical engineering of our university, based on the previous research, realized the sequential activation of N₂and CO₂to prepare multiple N− C bonds at room temperature. Here, we found that this coupling reaction can be realized by a quaternary anion AuNbBO⁻at room temperature. AuNbBO⁻can cleave the N ≡ N triple bond in N₂and two C=""O"" double bonds in CO₂to form a new product NCNBO⁻. To our knowledge, NCNBO⁻was synthesized by coupling N₂and CO₂for the first time. Compared with Nb₂BO⁻/N₂and NbBO⁻/N₂systems, the presence of Au atoms in AuNbBO⁻is essential for the direct coupling of N2 and CO₂, because Au atoms can reduce the active orbital energy of AuNbBO⁻to promote the π electron feedback between AuNbBO⁻and N₂. This is the second example of gas-phase clusters that realize the activation coupling of N₂and CO₂at room temperature. This work follows a new N₂activation mode previously proposed by us - metal ligand activation (Metal-Ligand Activation，MLA). This reaction model will help to develop new strategies for designing single metal atom catalysts.

Author profile attached:

Ma Jiabi, associate professor and doctoral supervisor, School of Chemistry and Chemical Engineering, Beijing Institute of Technology. Presided over the national key R & D plan (Youth Project), the major research plan (cultivation project) of the National Natural Science Foundation, etc. Already in J. am Chem. Soc.、Angew. Chem. Int. Ed.、J. Phys. Chem. Lett. He has published more than 40 SCI papers, including one on science as a collaborator.

Paper related links:https://pubs.acs.org/doi/10.1021/acs.jpclett.1c03774