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Experimental and Computational Studies of Dinitrogen Activation and Hydrogenation at a Tetranuclear Titanium Imide/Hydride Framework

  • Takanori Shima
    Takanori Shima
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    More by Takanori Shima
    Orcidhttp://orcid.org/0000-0003-1813-0439
  • , 
  • Gen Luo
    Gen Luo
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
    More by Gen Luo
    Orcidhttp://orcid.org/0000-0002-5297-6756
  • , 
  • Shaowei Hu
    Shaowei Hu
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    More by Shaowei Hu
  • , 
  • Yi Luo*
    Yi Luo
    State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
    *[email protected]
    More by Yi Luo
    Orcidhttp://orcid.org/0000-0001-6390-8639
  • , and 
  • Zhaomin Hou*
    Zhaomin Hou
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
    *[email protected]
    More by Zhaomin Hou
    Orcidhttp://orcid.org/0000-0003-2841-5120
Cite this: J. Am. Chem. Soc. 2019, 141, 6, 2713–2720
Publication Date (Web):January 23, 2019
https://doi.org/10.1021/jacs.8b13341
Copyright © 2019 American Chemical Society
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    Abstract

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    The activation of N2 by a tetranuclear titanium(III) diimide/tetrahydride complex, [(Cp′Ti)4(μ3-NH)2(μ-H)4] (1) (Cp′ = C5Me4SiMe3), which was obtained by the reaction of the Cp′-ligated titanium trialkyl complex Cp′Ti(CH2SiMe3)3 with H2 and N2, was investigated in detail by experimental and density functional theory studies. The reaction of 1 in the solid state with N2 (1 atm) at 180 °C gave the dinitride/diimide complex [(Cp′Ti)4(μ3-N)2(μ3-NH)2] (2) through the incorporation, cleavage, and partial hydrogenation of one molecule of N2 and release of two molecules of H2. At 130 °C, the formation of 2 was not observed, but instead, dehydrogenation of 1 took place through cleavage of the N–H bond in an imide ligand, followed by deprotonation of the other imide ligand with a hydride ligand, affording the dinitride/tetrahydride complex [(Cp′Ti)4(μ3-N)2(μ-H)4] (3). Upon heating under N2 (1 atm) at 180 °C, 3 was quantitatively converted to the dinitride/diimide complex 2. This transformation was initiated by migration of a hydride ligand to a nitride ligand to give one imide unit, followed by N2 coordination to a Ti atom and H2 release through the reductive elimination of two hydride ligands. The other imide ligand in 2 was formed by hydride migration to one of the two nitride ligands generated through the cleavage of the newly incorporated N2 unit. The hydrogenation of 2 with H2 (100 atm) at 180 °C afforded the tetraimide complex [(Cp′Ti)4(μ3-NH)4] (4). This reaction was initiated by σ-bond metathesis between H2 and a titanium–nitride bond, followed by migration of the resulting hydride ligand to the remaining nitride ligand. In all of these transformations, the interplay among the hydride, imide, and nitride ligands, including the reversible dehydrogenation/hydrogenation of imide and nitride species, at the multimetallic titanium framework has a critically important role.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.8b13341.

    • X-ray crystallographic data for 3 (CCDC 1862473) and 4 (CCDC 1862474) (CIF)

    • Experimental details, spectroscopic and analytical data, and DFT calculations, including Figures S1–S32 and Tables S1–S4 (PDF)

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