Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN3P-Mo(V) Nitride Complex: Significant Enhancement via Ligand Postmodification

Delong Han; Priyanka Chakraborty; Mei-Hui Huang; Li Yang; Hao Huang; Théo P. Gonçalves; Abdul Hamid Emwas; Zhiping Lai; Jr-Hau He; Aleksander Shkurenko; Mohamed Eddaoudi; Kuo-Wei Huang

doi:10.31635/ccschem.022.202202385

Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN³P-Mo(V) Nitride Complex: Significant Enhancement via Ligand Postmodification

Delong Han, Priyanka Chakraborty, Mei-Hui Huang, Li Yang, Hao Huang, Théo P. Gonçalves, Abdul Hamid Emwas, Zhiping Lai, Jr-Hau He, Aleksander Shkurenko, Mohamed Eddaoudi, Kuo-Wei Huang^*

^*Corresponding author for this work

Department of Materials Science and Engineering

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

5 Citations (Scopus)

Abstract

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 mainly focused on alternating ligands and metals. Herein, we report that the activity and stability of a PN³P-Mo pincer complex (2) toward dinitrogen (N₂) reduction were greatly enhanced through post-modification of the PN³P-Mo 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, when supported by an anionic pincer ligand, 2 furnished a high oxidation state Mo(V)-nitride complex via N₂ cleavage as a plausible key intermediate in the catalytic process, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature. © 2023 The Author(s).

Original language	English
Pages (from-to)	616-623
Number of pages	8
Journal	CCS Chemistry
Volume	5
Issue number	3
Online published	6 Dec 2022
DOIs	https://doi.org/10.31635/ccschem.022.202202385
Publication status	Published - Mar 2023

Research Keywords

molybdenum
PN3P
samarium(II) iodide
nitrogen reduction
ligand postmodification

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Han, 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. (2023). Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN³P-Mo(V) Nitride Complex: Significant Enhancement via Ligand Postmodification. CCS Chemistry, 5(3), 616-623. https://doi.org/10.31635/ccschem.022.202202385

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title = "Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN3P-Mo(V) Nitride Complex: Significant Enhancement via Ligand Postmodification",

abstract = "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 mainly focused on alternating ligands and metals. Herein, we report that the activity and stability of a PN3P-Mo pincer complex (2) toward dinitrogen (N2) reduction were greatly enhanced through post-modification of the PN3P-Mo 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, when supported by an anionic pincer ligand, 2 furnished a high oxidation state Mo(V)-nitride complex via N2 cleavage as a plausible key intermediate in the catalytic process, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature. {\textcopyright} 2023 The Author(s).",

keywords = "molybdenum, PN3P, samarium(II) iodide, nitrogen reduction, ligand postmodification",

author = "Delong Han and Priyanka Chakraborty and Mei-Hui Huang and Li Yang and Hao Huang and Gon{\c c}alves, {Th{\'e}o P.} and Emwas, {Abdul Hamid} and Zhiping Lai and Jr-Hau He and Aleksander Shkurenko and Mohamed Eddaoudi and Kuo-Wei Huang",

year = "2023",

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doi = "10.31635/ccschem.022.202202385",

language = "English",

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Han, D, Chakraborty, P, Huang, M-H, Yang, L, Huang, H, Gonçalves, TP, Emwas, AH, Lai, Z, He, J-H, Shkurenko, A, Eddaoudi, M & Huang, K-W 2023, 'Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN³P-Mo(V) Nitride Complex: Significant Enhancement via Ligand Postmodification', CCS Chemistry, vol. 5, no. 3, pp. 616-623. https://doi.org/10.31635/ccschem.022.202202385

TY - JOUR

T1 - Nitrogen Reduction to Ammonia by a Phosphorus-Nitrogen PN3P-Mo(V) Nitride Complex

T2 - Significant Enhancement via Ligand Postmodification

AU - Han, Delong

AU - Chakraborty, Priyanka

AU - Huang, Mei-Hui

AU - Yang, Li

AU - Huang, Hao

AU - Gonçalves, Théo P.

AU - Emwas, Abdul Hamid

AU - Lai, Zhiping

AU - He, Jr-Hau

AU - Shkurenko, Aleksander

AU - Eddaoudi, Mohamed

AU - Huang, Kuo-Wei

PY - 2023/3

Y1 - 2023/3

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 mainly focused on alternating ligands and metals. Herein, we report that the activity and stability of a PN3P-Mo pincer complex (2) toward dinitrogen (N2) reduction were greatly enhanced through post-modification of the PN3P-Mo 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, when supported by an anionic pincer ligand, 2 furnished a high oxidation state Mo(V)-nitride complex via N2 cleavage as a plausible key intermediate in the catalytic process, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature. © 2023 The Author(s).

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 mainly focused on alternating ligands and metals. Herein, we report that the activity and stability of a PN3P-Mo pincer complex (2) toward dinitrogen (N2) reduction were greatly enhanced through post-modification of the PN3P-Mo 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, when supported by an anionic pincer ligand, 2 furnished a high oxidation state Mo(V)-nitride complex via N2 cleavage as a plausible key intermediate in the catalytic process, suggesting a catalytic cycle that may involve different oxidation states (II/V) from those with 10-π electron configuration in the literature. © 2023 The Author(s).

KW - molybdenum

KW - PN3P

KW - samarium(II) iodide

KW - nitrogen reduction

KW - ligand postmodification

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U2 - 10.31635/ccschem.022.202202385

DO - 10.31635/ccschem.022.202202385

M3 - RGC 21 - Publication in refereed journal

SN - 2096-5745

VL - 5

SP - 616

EP - 623

JO - CCS Chemistry

JF - CCS Chemistry

IS - 3

ER -