Synthesis and reactivity of iron–dinitrogen complexes bearing anionic methyl- and phenyl-substituted pyrrole-based PNP-type pincer ligands toward catalytic nitrogen fixation

2017 ◽  
Vol 53 (88) ◽  
pp. 12040-12043 ◽  
Author(s):  
Yoshiya Sekiguchi ◽  
Shogo Kuriyama ◽  
Aya Eizawa ◽  
Kazuya Arashiba ◽  
Kazunari Nakajima ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Effective Catalyst ◽  
Dinitrogen Complexes ◽  
Dinitrogen Complex

Newly designed and prepared iron–dinitrogen complex is found to work as a more effective catalyst toward catalytic nitrogen fixation.

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.

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.

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

Chemical nitrogen fixation by using molybdenum and tungsten complexes

2001 ◽  
Vol 73 (2) ◽  
pp. 261-263 ◽  
Author(s):  
Masanobu Hidai ◽  
Yasushi Mizobe
Keyword(s):  
Nitrogen Fixation ◽  
The Other ◽  
Nucleophilic Attack ◽  
Dinuclear Complexes ◽  
Tungsten Complexes ◽  
Other Hand ◽  
Dinitrogen Complexes ◽  
Dinitrogen Complex ◽  
Moderate Yield ◽  
And Tungsten

Dinitrogen complex cis-[W (N2) 2 (PMe2Ph) 4] reacts with an excess of acidic dihydrogen complexes such as trans-[RuCl (h2-H2) (dppe) 2]BF4 (dppe = 1,2-bis (diphenylphosphino) ethane) at 55 °C under 1 atm of H2 to form ammonia in moderate yield. The reaction is presumed to proceed through nucleophilic attack of the remote nitrogen of the coordinated dinitrogen on the dihydrogen ligand. The coordinated dinitrogen is also protonated by treatment with hydrosulfido-bridged dinuclear complexes such as [Cp*Ir (m-SH) 3IrCp*]Cl (Cp* = h5-C5Me5) to afford ammonia. On the other hand, the synthetic cycle for the formation of pyrrole and N-aminopyrrole from dinitrogen and 2,5-dimethoxytetrahydrofuran has been established starting from dinitrogen complexes of the type trans-[M (N2) 2 (dppe) 2 ] (M = Mo, W).

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

Front Cover: Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation (Eur. J. Inorg. Chem. 32/2017)

2017 ◽  
Vol 2017 (32) ◽  
pp. 3767-3767
Author(s):  
Ryuji Imayoshi ◽  
Kazunari Nakajima ◽  
Jun Takaya ◽  
Nobuharu Iwasawa ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Front Cover ◽  
Dinitrogen Complexes

Synthesis and reactivity of titanium- and zirconium-dinitrogen complexes bearing anionic pyrrole-based PNP-type pincer ligands

2018 ◽  
Vol 47 (33) ◽  
pp. 11322-11326 ◽  
Author(s):  
Yoshiya Sekiguchi ◽  
Fanqiang Meng ◽  
Hiromasa Tanaka ◽  
Aya Eizawa ◽  
Kazuya Arashiba ◽  
...  
Keyword(s):  
Pincer Ligands ◽  
X Ray ◽  
Dinitrogen Complexes

Dinitrogen-bridged dititanium and dizirconium complexes bearing anionic pyrrole-based PNP-type pincer ligands are prepared and characterized by X-ray analysis.

Synthesis and Protonation of Molybdenum– and Tungsten–Dinitrogen Complexes Bearing PNP-Type Pincer Ligands

2012 ◽  
Vol 31 (5) ◽  
pp. 2035-2041 ◽  
Author(s):  
Kazuya Arashiba ◽  
Kouitsu Sasaki ◽  
Shogo Kuriyama ◽  
Yoshihiro Miyake ◽  
Haruyuki Nakanishi ◽  
...  
Keyword(s):  
Pincer Ligands ◽  
Dinitrogen Complexes ◽  
And Tungsten

Early developments in lanthanide-based dinitrogen reduction chemistry

2005 ◽  
Vol 83 (4) ◽  
pp. 375-384 ◽  
Author(s):  
William J Evans ◽  
David S Lee
Keyword(s):  
Nitrogen Fixation ◽  
Alkali Metal ◽  
Key Words ◽  
Entire Series ◽  
Dinitrogen Reduction ◽  
Dinitrogen Complex

Although the first crystallographically characterized lanthanide dinitrogen complex was reported in 1988 with samarium, it is only in recent years that this field has expanded to include fully characterized examples for the entire series of lanthanides. The development of lanthanide dinitrogen chemistry has been aided by a series of unexpected results that present some good lessons in the development of science. This review presents a chronological account of the lanthanide dinitrogen chemistry discovered in our laboratory through the summer of 2004.Key words: lanthanides, dinitrogen, reduction, alkali metal, nitrogen fixation, diazenido.

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