TY - JOUR
T1 - Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN3PMo(V) Nitride Complex: Significant Enhancement via Ligand Post-Modification
AU - Han, Delong
AU - Chakraborty, Priyanka
AU - Huang, Mei-Hui
AU - Yang, Li
AU - Huang, Hao
AU - Goncalves, Theo
AU - Emwas, Abdul-Hamid M.
AU - Lai, Zhiping
AU - He, Jr-Hau
AU - Shkurenko, Aleksander
AU - Eddaoudi, Mohamed
AU - Huang, Kuo-Wei
N1 - KAUST Repository Item: Exported on 2022-11-16
Acknowledgements: We are grateful to the service of NOOR 2, Shaheen 2 High-Performance Computing Facilities, and financial support from King Abdullah University of Science and Technology (KAUST). Dr. Xingzhu Chen and Amy Perez are acknowledged for the graphic design.
PY - 2022/11/11
Y1 - 2022/11/11
N2 - Efforts to develop organometallic complexes for catalytic nitrogen reduction have seen significant progress in recent years. However, the strategies for improving the activity of the homogenous catalysts have been mainly focused on alternating ligands and metals so far. Herein, we report that the activity and stability of a PN3P-Mo pincer complex ( 2) toward dinitrogen (N2) reduction were greatly enhanced through the post-modification of the PN3P pincer framework of its parent complex ( 1). A high ratio of NH3/Mo (3525) was achieved in the presence of SmI2 as a reductant. In sharp contrast, 1 only afforded an NH3/Mo ratio of 21. Moreover, since supported by the anionic pincer ligand, 2 furnished a high oxidation state Mo(V) nitride complex as a plausible key intermediate in the catalytic process via N2-cleavage, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature.
AB - Efforts to develop organometallic complexes for catalytic nitrogen reduction have seen significant progress in recent years. However, the strategies for improving the activity of the homogenous catalysts have been mainly focused on alternating ligands and metals so far. Herein, we report that the activity and stability of a PN3P-Mo pincer complex ( 2) toward dinitrogen (N2) reduction were greatly enhanced through the post-modification of the PN3P pincer framework of its parent complex ( 1). A high ratio of NH3/Mo (3525) was achieved in the presence of SmI2 as a reductant. In sharp contrast, 1 only afforded an NH3/Mo ratio of 21. Moreover, since supported by the anionic pincer ligand, 2 furnished a high oxidation state Mo(V) nitride complex as a plausible key intermediate in the catalytic process via N2-cleavage, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature.
UR - http://hdl.handle.net/10754/685756
UR - http://www.chinesechemsoc.org/doi/10.31635/ccschem.022.202202385
U2 - 10.31635/ccschem.022.202202385
DO - 10.31635/ccschem.022.202202385
M3 - Article
SN - 2096-5745
SP - 1
EP - 39
JO - CCS Chemistry
JF - CCS Chemistry
ER -