Synthesis and Catalytic Reactivity of Bis(molybdenum-trihalide) Complexes Bridged by Ferrocene Skeleton toward Catalytic Nitrogen Fixation

Takayuki Itabashi, Kazuya Arashiba, Hiromasa Tanaka, Asuka Konomi, Aya Eizawa, Kazunari Nakajima, Kazunari Yoshizawa, Yoshiaki Nishibayashi

Research output: Contribution to journalArticle

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Abstract

Bis(molybdenum-trihalide) complexes bearing PNP-type pincer ligand bridged by ferrocene skeleton are synthesized and characterized by X-ray analysis. Ferrocene-linked bis(molybdenum-trihalide) complexes have a lower catalytic activity than do the corresponding mononuclear molybdenum trihalide complexes under the same reaction conditions. The cyclic voltammetry of ferrocene-linked bis(molybdenum-trichloride) complex shows an electronic interaction between the molybdenum and iron centers, but no electronic interaction between the two molybdenum centers is observed in the ferrocene-linked bis(molybdenum-trichloride) complex. Density functional theory calculations indicate no formation of an intramolecular dinitrogen-bridged dimolybdenum structure in the ferrocene-linked bismolybdenum complexes bearing PNP-type pincer ligands.

Original languageEnglish
Pages (from-to)2863-2872
Number of pages10
JournalOrganometallics
Volume38
Issue number14
DOIs
Publication statusPublished - Jul 22 2019

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Nitrogen fixation
nitrogenation
Molybdenum
musculoskeletal system
molybdenum
reactivity
synthesis
Bearings (structural)
chlorides
Ligands
ligands
X ray analysis
ferrocene
electronics
Cyclic voltammetry
Density functional theory
catalytic activity
Catalyst activity
Iron
interactions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Synthesis and Catalytic Reactivity of Bis(molybdenum-trihalide) Complexes Bridged by Ferrocene Skeleton toward Catalytic Nitrogen Fixation. / Itabashi, Takayuki; Arashiba, Kazuya; Tanaka, Hiromasa; Konomi, Asuka; Eizawa, Aya; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki.

In: Organometallics, Vol. 38, No. 14, 22.07.2019, p. 2863-2872.

Research output: Contribution to journalArticle

Itabashi, Takayuki ; Arashiba, Kazuya ; Tanaka, Hiromasa ; Konomi, Asuka ; Eizawa, Aya ; Nakajima, Kazunari ; Yoshizawa, Kazunari ; Nishibayashi, Yoshiaki. / Synthesis and Catalytic Reactivity of Bis(molybdenum-trihalide) Complexes Bridged by Ferrocene Skeleton toward Catalytic Nitrogen Fixation. In: Organometallics. 2019 ; Vol. 38, No. 14. pp. 2863-2872.
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abstract = "Bis(molybdenum-trihalide) complexes bearing PNP-type pincer ligand bridged by ferrocene skeleton are synthesized and characterized by X-ray analysis. Ferrocene-linked bis(molybdenum-trihalide) complexes have a lower catalytic activity than do the corresponding mononuclear molybdenum trihalide complexes under the same reaction conditions. The cyclic voltammetry of ferrocene-linked bis(molybdenum-trichloride) complex shows an electronic interaction between the molybdenum and iron centers, but no electronic interaction between the two molybdenum centers is observed in the ferrocene-linked bis(molybdenum-trichloride) complex. Density functional theory calculations indicate no formation of an intramolecular dinitrogen-bridged dimolybdenum structure in the ferrocene-linked bismolybdenum complexes bearing PNP-type pincer ligands.",
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AU - Itabashi, Takayuki

AU - Arashiba, Kazuya

AU - Tanaka, Hiromasa

AU - Konomi, Asuka

AU - Eizawa, Aya

AU - Nakajima, Kazunari

AU - Yoshizawa, Kazunari

AU - Nishibayashi, Yoshiaki

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N2 - Bis(molybdenum-trihalide) complexes bearing PNP-type pincer ligand bridged by ferrocene skeleton are synthesized and characterized by X-ray analysis. Ferrocene-linked bis(molybdenum-trihalide) complexes have a lower catalytic activity than do the corresponding mononuclear molybdenum trihalide complexes under the same reaction conditions. The cyclic voltammetry of ferrocene-linked bis(molybdenum-trichloride) complex shows an electronic interaction between the molybdenum and iron centers, but no electronic interaction between the two molybdenum centers is observed in the ferrocene-linked bis(molybdenum-trichloride) complex. Density functional theory calculations indicate no formation of an intramolecular dinitrogen-bridged dimolybdenum structure in the ferrocene-linked bismolybdenum complexes bearing PNP-type pincer ligands.

AB - Bis(molybdenum-trihalide) complexes bearing PNP-type pincer ligand bridged by ferrocene skeleton are synthesized and characterized by X-ray analysis. Ferrocene-linked bis(molybdenum-trihalide) complexes have a lower catalytic activity than do the corresponding mononuclear molybdenum trihalide complexes under the same reaction conditions. The cyclic voltammetry of ferrocene-linked bis(molybdenum-trichloride) complex shows an electronic interaction between the molybdenum and iron centers, but no electronic interaction between the two molybdenum centers is observed in the ferrocene-linked bis(molybdenum-trichloride) complex. Density functional theory calculations indicate no formation of an intramolecular dinitrogen-bridged dimolybdenum structure in the ferrocene-linked bismolybdenum complexes bearing PNP-type pincer ligands.

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