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The Beijing Institute of Technology team has made important progress in the field of gas-phase cluster chemistry

Recently, Ma Jiabi, associate professor of North Institute of chemistry and chemical engineering, conducted an in-depth study on the reactivity and structure of N2 and CO2 with aunbbo − gas-phase clusters through the combination of mass spectrometry experiment and theoretical chemical calculation, and realized the direct coupling of N2 and CO2 to form two N − C bonds at room temperature, and follow a new N2 activation 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.

N2 and CO2 are very inert small molecules. It is very challenging to activate and couple N2 and CO2 under 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 N2 molecules 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 NbH2clusters at room temperature, and realized the preparation of C−N bonds from N2 and 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 N2 to 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 N2 and 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 N2 and CO2 to 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 N2 and two C=""O"" double bonds in CO2 to form a new product NCNBO. To our knowledge, NCNBO was synthesized by coupling N2 and CO2 for the first time. Compared with Nb2BO/N2 and NbBO/N2 systems, 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 N2 and CO2 at room temperature. This work follows a new N2 activation 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