ChemInform Abstract: New Developments in Synthetic Nitrogen Fixation with Molybdenum and Tungsten Phosphine Complexes

ChemInform ◽  
2010 ◽  
Vol 41 (51) ◽  
pp. no-no
Author(s):  
Ameli Dreher ◽  
Gerald Stephan ◽  
Felix Tuczek
Keyword(s):  
Nitrogen Fixation ◽  
New Developments ◽  
Phosphine Complexes ◽  
And Tungsten

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.

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