Preparation and reactivity of iron complexes bearing anionic carbazole-based PNP-type pincer ligands toward catalytic nitrogen fixation

2018 ◽  
Vol 47 (4) ◽  
pp. 1117-1121 ◽  
Author(s):  
Junichi Higuchi ◽  
Shogo Kuriyama ◽  
Aya Eizawa ◽  
Kazuya Arashiba ◽  
Kazunari Nakajima ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Iron Complexes ◽  
Pincer Ligands

Newly prepared iron complexes bearing carbazole-based PNP-type pincer ligands are found to work as catalysts toward nitrogen fixation.

Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation

2017 ◽  
Vol 2017 (32) ◽  
pp. 3769-3778 ◽  
Author(s):  
Ryuji Imayoshi ◽  
Kazunari Nakajima ◽  
Jun Takaya ◽  
Nobuharu Iwasawa ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Dinitrogen Complexes

Ligand Abstraction in the Reaction of Aryldiazonium Ions with some Iron Complexes Containing Coordinated Cysteine, Maleonitriledithiol, or Triarylphosphine

1974 ◽  
Vol 52 (10) ◽  
pp. 1914-1922 ◽  
Author(s):  
James A. Carroll ◽  
David R. Fisher ◽  
Geoffrey W. Rayner Canham ◽  
Derek Sutton
Keyword(s):  
Nitrogen Fixation ◽  
Raman Spectra ◽  
Biological Nitrogen Fixation ◽  
Iron Complexes ◽  
Detailed Comparison ◽  
A Site ◽  
Biological Nitrogen ◽  
Extrusion Product

The reactions of selected aryldiazonium tetrafluoroborates with Fe(CO)3(PR3)2, [Fe(mnt)2]−, [Fe(cystH)2]2+, and [Fe(CO)2(cyst)2] (mnt = S2C2(CN)2, cyst = SCH2CH(NH2)CO2H ) result in abstraction of the ligand to yield arenediazophosphonium ions, S-(arenediazo)cysteine or the dinitrogen extrusion product ArS(CN)C=C(CN)SAr. Arylazo complexes of iron were not obtained. The products have been characterized and compounds related to S-(arenediazo)cysteine, namely S-(arenediazo)triphenylmethyl mercaptan and S-(arenediazo)sulfones, have been synthesized for a detailed comparison of their Raman spectra. Assignments of ν(N=N) are made on the basis of 15N- and 2H-substitution experiments. The possible involvement of nucleophilic sulfur as a site for the activation and or reduction of complexed dinitrogen in biological nitrogen fixation is proposed.

scholarly journals Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation

2017 ◽  
Vol 2017 (32) ◽  
pp. 3768-3768 ◽  
Author(s):  
Ryuji Imayoshi ◽  
Kazunari Nakajima ◽  
Jun Takaya ◽  
Nobuharu Iwasawa ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Dinitrogen Complexes

Azaferrocene-Based PNP-Type Pincer Ligand: Synthesis of Molybdenum, Chromium, and Iron Complexes and Reactivity toward Nitrogen Fixation

2016 ◽  
Vol 2016 (30) ◽  
pp. 4856-4861 ◽  
Author(s):  
Shogo Kuriyama ◽  
Kazuya Arashiba ◽  
Kazunari Nakajima ◽  
Hiromasa Tanaka ◽  
Kazunari Yoshizawa ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Iron Complexes ◽  
Pincer Ligand ◽  
Ligand Synthesis

Effect of substituents on molybdenum triiodide complexes bearing PNP-type pincer ligands toward catalytic nitrogen fixation

2019 ◽  
Vol 48 (10) ◽  
pp. 3182-3186 ◽  
Author(s):  
Takayuki Itabashi ◽  
Ikki Mori ◽  
Kazuya Arashiba ◽  
Aya Eizawa ◽  
Kazunari Nakajima ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Ammonia Production ◽  
Reaction Conditions ◽  
Effect Of Substituents

Molybdenum triiodide complexes bearing phenyl and ferrocenyl substituted PNP-type pincer ligands acted as more effective catalysts toward ammonia production under ambient reaction conditions.

scholarly journals Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

2020 ◽  
Author(s):  
Fanqiang Meng ◽  
Shogo Kuriyama ◽  
Hiromasa Tanaka ◽  
Akihito Egi ◽  
Kazunari Yoshizawa ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Pincer Ligand ◽  
Reaction Conditions ◽  
Rhenium Atom ◽  
Phosphine Complexes ◽  
Proton Source ◽  
Dinitrogen Complexes ◽  
Dinitrogen Complex ◽  
Ammonia Formation

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC<sub>8</sub> as a reductant and [HPCy<sub>3</sub>]BAr<sup>F</sup><sub>4</sub> (Cy = cyclohexyl, Ar<sup>F</sup> = 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC<sub>8</sub> as a reductant and Me<sub>3</sub>SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

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