Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN3PMo(V) Nitride Complex: Significant Enhancement via Ligand Post-Modification
Emwas, Abdul-Hamid M.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Chemical Engineering Program
Chemical Science Program
Computer, Electrical and Mathematical Science and Engineering (CEMSE) Division
Core Lab, King Abdullah University of Science and Technology, Thuwal 23955
Functional Materials Design, Discovery and Development (FMD3)
Homogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/685756
MetadataShow full item record
AbstractEfforts 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.
CitationHan, D., Chakraborty, P., Huang, M.-H., Yang, L., Huang, H., Gonçalves, T. P., Emwas, A. H., Lai, Z., He, J.-H., Shkurenko, A., Eddaoudi, M., & Huang, K.-W. (2022). Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN 3 PMo(V) Nitride Complex: Significant Enhancement via Ligand Post-Modification. CCS Chemistry, 1–39. https://doi.org/10.31635/ccschem.022.202202385
SponsorsWe 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.
PublisherChinese Chemical Society
CollectionsArticles; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3); Chemical Science Program; Chemical Engineering Program; KAUST Catalysis Center (KCC); Computer, Electrical and Mathematical Science and Engineering (CEMSE) Division
Except where otherwise noted, this item's license is described as Archived with thanks to CCS Chemistry under a Creative Commons license, details at: https://creativecommons.org/licenses/by-nc/4.0/