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(n-Bu)4NBr-Promoted N2 Splitting to Molybdenum Nitride
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    (n-Bu)4NBr-Promoted N2 Splitting to Molybdenum Nitride
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    • Dan-Dan Zhai
      Dan-Dan Zhai
      Department of Chemistry, Fudan University, Shanghai 200438, China
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    • Shuo-Qing Zhang
      Shuo-Qing Zhang
      Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
    • Si-Jun Xie
      Si-Jun Xie
      Department of Chemistry, Fudan University, Shanghai 200438, China
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    • Rong-Kai Wu
      Rong-Kai Wu
      Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
      More by Rong-Kai Wu
    • Feng Liu
      Feng Liu
      Department of Chemistry, Fudan University, Shanghai 200438, China
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    • Zhen-Feng Xi
      Zhen-Feng Xi
      Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
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    • Xin Hong*
      Xin Hong
      Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
      Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, Hangzhou 310024, China
      Beijing National Laboratory for Molecular Sciences, Zhongguancun North First Street No. 2, Beijing 100190, PR China
      *Email: [email protected]
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    • Zhang-Jie Shi*
      Zhang-Jie Shi
      Department of Chemistry, Fudan University, Shanghai 200438, China
      *Email: [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 31, 14071–14078
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    https://doi.org/10.1021/jacs.2c01507
    Published July 26, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Splitting of N2 via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N2 fixation. However, most N2 splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N2, which is often incompatible with functionalizing agents. Catalytic and sustainable N2 splitting to produce metal nitrides under mild conditions may create efficient and straightforward methods for N-containing organic compounds. Herein, we present that a readily available and nonredox (n-Bu)4NBr can promote N2-splitting with a Mo(III) platform. Both experimental and theoretical mechanistic studies suggest that simple X (X = Br, Cl, etc.) anions could induce the disproportionation of MoIII[N(TMS)Ar]3 at the early stage of the catalysis to generate a catalytically active {MoII[N(TMS)Ar]3} species. The quintet MoII species prove to be more favorable for N2 fixation kinetically and thermodynamically, compared with the quartet MoIII counterpart. Especially, computational studies reveal a distinct heterovalent {MoII–N2–MoIII} dimeric intermediate for the N≡N triple bond cleavage.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c01507.

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    CCDC 2126073, 2126133, and 2126164 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

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    This article is cited by 3 publications.

    1. Daniel Rütter, Maurice van Gastel, Markus Leutzsch, Nils Nöthling, Daniel SantaLucia, Frank Neese, Alois Fürstner. Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer. Inorganic Chemistry 2024, 63 (18) , 8376-8389. https://doi.org/10.1021/acs.inorgchem.4c00762
    2. Zhaoxin Li, Chenrui Liu, Jingyi An, Xi Wang, Shaowei Hu. Catalytic Dinitrogen Reduction to Silylamines by Molybdenum Nitride Complexes Bearing a Diphenolate N-Heterocyclic Carbene Ligand. ACS Catalysis 2024, 14 (9) , 6558-6564. https://doi.org/10.1021/acscatal.4c00307
    3. Chaoyue Zhao, Rongkai Wu, Shuoqing Zhang, Xin Hong. Benchmark Study of Density Functional Theory Methods in Geometry Optimization of Transition Metal–Dinitrogen Complexes. The Journal of Physical Chemistry A 2023, 127 (32) , 6791-6803. https://doi.org/10.1021/acs.jpca.3c04215

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 31, 14071–14078
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c01507
    Published July 26, 2022
    Copyright © 2022 American Chemical Society

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