Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation

Aya Eizawa, Kazuya Arashiba, Hiromasa Tanaka, Shogo Kuriyama, Yuki Matsuo, Kazunari Nakajima, Kazunari Yoshizawa, Yoshiaki Nishibayashi

研究成果: ジャーナルへの寄稿記事

59 引用 (Scopus)

抄録

Intensive efforts for the transformation of dinitrogen using transition metal-dinitrogen complexes as catalysts under mild reaction conditions have been made. However, limited systems have succeeded in the catalytic formation of ammonia. Here we show that newly designed and prepared dinitrogen-bridged dimolybdenum complexes bearing N-heterocyclic carbene-And phosphine-based PCP-pincer ligands [{Mo(N 2) 2 (PCP)} 2 (μ-N 2)] (1) work as so far the most effective catalysts towards the formation of ammonia from dinitrogen under ambient reaction conditions, where up to 230 equiv. of ammonia are produced based on the catalyst. DFT calculations on 1 reveal that the PCP-pincer ligand serves as not only a strong σ-donor but also a I €-Acceptor. These electronic properties are responsible for a solid connection between the molybdenum centre and the pincer ligand, leading to the enhanced catalytic activity for nitrogen fixation.

元の言語英語
記事番号14874
ジャーナルNature communications
8
DOI
出版物ステータス出版済み - 4 4 2017
外部発表Yes

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Bearings (structural)
Nitrogen fixation
nitrogenation
Nitrogen Fixation
Ammonia
catalytic activity
ammonia
Catalyst activity
phosphine
Ligands
catalysts
ligands
Catalysts
Molybdenum
Coordination Complexes
carbenes
Metal complexes
phosphines
Discrete Fourier transforms
Electronic properties

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

これを引用

Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation. / Eizawa, Aya; Arashiba, Kazuya; Tanaka, Hiromasa; Kuriyama, Shogo; Matsuo, Yuki; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki.

:: Nature communications, 巻 8, 14874, 04.04.2017.

研究成果: ジャーナルへの寄稿記事

Eizawa, Aya ; Arashiba, Kazuya ; Tanaka, Hiromasa ; Kuriyama, Shogo ; Matsuo, Yuki ; Nakajima, Kazunari ; Yoshizawa, Kazunari ; Nishibayashi, Yoshiaki. / Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation. :: Nature communications. 2017 ; 巻 8.
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abstract = "Intensive efforts for the transformation of dinitrogen using transition metal-dinitrogen complexes as catalysts under mild reaction conditions have been made. However, limited systems have succeeded in the catalytic formation of ammonia. Here we show that newly designed and prepared dinitrogen-bridged dimolybdenum complexes bearing N-heterocyclic carbene-And phosphine-based PCP-pincer ligands [{Mo(N 2) 2 (PCP)} 2 (μ-N 2)] (1) work as so far the most effective catalysts towards the formation of ammonia from dinitrogen under ambient reaction conditions, where up to 230 equiv. of ammonia are produced based on the catalyst. DFT calculations on 1 reveal that the PCP-pincer ligand serves as not only a strong σ-donor but also a I €-Acceptor. These electronic properties are responsible for a solid connection between the molybdenum centre and the pincer ligand, leading to the enhanced catalytic activity for nitrogen fixation.",
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AU - Eizawa, Aya

AU - Arashiba, Kazuya

AU - Tanaka, Hiromasa

AU - Kuriyama, Shogo

AU - Matsuo, Yuki

AU - Nakajima, Kazunari

AU - Yoshizawa, Kazunari

AU - Nishibayashi, Yoshiaki

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