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).

Research inspired by the chemistry of nitrogenase — Novel metal complexes and their reactivity toward dinitrogen, nitriles, and alkynes

2005 ◽  
Vol 83 (4) ◽  
pp. 358-374 ◽  
Author(s):  
Masanobu Hidai ◽  
Yasushi Mizobe
Keyword(s):  
Nitrogen Fixation ◽  
Metal Complexes ◽  
Active Site ◽  
Bond Cleavage ◽  
Catalytic Reactions ◽  
Tertiary Phosphine ◽  
Tertiary Phosphines ◽  
Dinitrogen Complexes ◽  
And Tungsten

Summarized here are our continuous studies of the last three decades concerning syntheses of new types of complexes learned from nitrogenase and their reactivites toward dinitrogen, nitriles, and alkynes. For Mo and W dinitrogen complexes with tertiary phosphine coligands, a variety of their intriguing reactivities have been demonstrated, and novel transformations of the N2 ligands into numerous nitrogen-containing ligands and compounds have been developed. The C≡N bond cleavage of certain nitriles also proceeds on the Mo site surrounded by tertiary phosphines. Stimulated by the sophisticated structure of the active site of nitrogenase, multinuclear metal–sulfur complexes have been synthesized in rational ways. New types of stoichiometric and catalytic reactions of alkynes have been found by using the thiolato-bridged diruthenium complexes and some cubane-type sulfido clusters containing a noble metal.Key words: nitrogen fixation, molybdenum and tungsten dinitrogen complexes, ruthenium thiolato complexes, metal sulfido clusters, nitriles, alkynes.

scholarly journals Nitrogen Fixation. II. On the Charge Distribution in Dinitrogen Complexes of Rhenium, Molybdenum and Tungsten.

1980 ◽  
Vol 34a ◽  
pp. 483-494 ◽  
Author(s):  
Abdul Malek ◽  
Börje Folkesson ◽  
Ragnar Larsson ◽  
E. Tørneng ◽  
T. Woldbæk ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Charge Distribution ◽  
Dinitrogen Complexes ◽  
And Tungsten

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–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.

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