Nitrogen reduction by the Fe sites of synthetic [Mo₃S₄Fe] cubes

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  • Ohki, Yasuhiro
    Institute for Chemical Research, Kyoto University
  • Munakata, Kenichiro
    Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University
  • Matsuoka, Yuto
    Institute for Chemical Research, Kyoto University
  • Hara, Ryota
    Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University
  • Kachi, Mami
    Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University
  • Uchida, Keisuke
    Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University
  • Tada, Mizuki
    Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University
  • Cramer, Roger E.
    Department of Chemistry, University of Hawaii
  • Sameera, W. M. C.
    Instituted of Low Temperature Science, Hokkaido University; Department of Chemistry, University of Colombo
  • Takayama, Tsutomu
    Department of Chemistry, Daido University
  • Sakai, Yoichi
    Department of Chemistry, Daido University
  • Kuriyama, Shogo
    Department of Applied Chemistry, School of Engineering, The University of Tokyo
  • Nishibayashi, Yoshiaki
    Department of Applied Chemistry, School of Engineering, The University of Tokyo
  • Tanifuji, Kazuki
    Institute for Chemical Research, Kyoto University

Abstract

Nitrogen (N₂) fixation by nature, which is a crucial process for the supply of bio-available forms of nitrogen, is performed by nitrogenase. This enzyme uses a unique transition-metal–sulfur–carbon cluster as its active-site co-factor ([(R-homocitrate)MoFe₇S₉C], FeMoco), and the sulfur-surrounded iron (Fe) atoms have been postulated to capture and reduce N₂ (refs.). Although there are a few examples of synthetic counterparts of the FeMoco, metal–sulfur cluster, which have shown binding of N₂ (refs.), the reduction of N₂ by any synthetic metal–sulfur cluster or by the extracted form of FeMoco has remained elusive, despite nearly 50 years of research. Here we show that the Fe atoms in our synthetic [Mo₃S₄Fe] cubes can capture a N₂ molecule and catalyse N₂ silylation to form N(SiMe₃)₃ under treatment with excess sodium and trimethylsilyl chloride. These results exemplify the catalytic silylation of N₂ by a synthetic metal–sulfur cluster and demonstrate the N₂-reduction capability of Fe atoms in a sulfur-rich environment, which is reminiscent of the ability of FeMoco to bind and activate N₂.

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Journal

  • Nature

    Nature 607 (7917), 86-90, 2022-07-07

    Springer Nature

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