Chemical Evidence concerning the Function of Molybdenum in Nitrogenase

Chatt, J.; Dilworth, J. R.; Richards, Raymond L.; Sanders, J. Roger

doi:10.1038/2241201a0

Cited by 49 publications

(22 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[16][17][18] Moreover, catalytic properties of Mo with respect to N 2 are known, for example, nitrogenase within bacteria using molybdenum enzymes as catalyst. 19 Catalytic N 2 dissociation on surfaces has been induced successfully for the electronically similar W(001), whereas growth properties of MgO are, however, unknown. [20][21][22] We have grown thin films of MgO:N on Mo(001) with thicknesses up to 10 monolayers (ML) at optimal doping.…”

Section: Introductionmentioning

confidence: 99%

Catalytic growth of N-doped MgO on Mo(001)

2012

View full text Add to dashboard Cite

A simple pathway to grow thin films of N-doped MgO (MgO:N), which has been found experimentally to be a ferromagnetic d 0 insulator, is presented. It relies on the catalytic properties of a Mo(001) substrate using the growth of Mg in a mixed atmosphere of O 2 and N 2 . Scanning tunneling spectroscopy reveals that the films are insulating and exhibit an N-induced state slightly below the conduction band minimum.

show abstract

Section: Introductionmentioning

confidence: 99%

Catalytic growth of N-doped MgO on Mo(001)

2012

View full text Add to dashboard Cite

show abstract

“…It is therefore extremely interesting that all of these iron complexes were recovered unchanged after attempts to reduce them catalytically with hydrogen even under more severe condition^.^ The Mo and W complexes reported by Trofimenko (4) are also resistant to hydrogenation, and we intend to examine further the apparently critical relationship of v(N2) with ease of hydrogenation. In this regard it is perhaps relevant that despite the fact that v(N2) in metal dinitrogen complexes may be lowered as far as 1630 cln-' by attachment of an acceptor atom M' to the terminal nitrogen atom to form a polynuclear M-N=N-M' bridge, such con~pounds have not been found to undergo reduction of the azo-function (12,13).…”

Section: Resultsmentioning

confidence: 99%

Models for the Interaction of Nitrogen with Transition Metals. Part III. Preparation and Properties of some Cationic Arylazo Complexes of Iron

Fisher¹,

Sutton²

1973

Can. J. Chem.

View full text Add to dashboard Cite

Fe(CO)3(PPh3)2 reacts with p-substituted aryl diazonium tetrafluoroborates to yield the compounds [Fe(CO)2(PPh3)2(N2C6H4X)]BF4 (where X = F, Cl, Br, H, NO2, OCH3, and OH but not NEt2). The complex cation displays properties consistent with replacement of an equatorial CO ligand in Fe(CO)3(PPh3)2 by the more effective π-acceptor ligand [N2C6H4X]+ analogous to NO+. A very strong band at ca. 1720 cm−1 in the i.r. spectrum due to v(N2) has been identified by 15N isotopic substitution. This value is much higher than for most other arylazo complexes yet prepared and the azo group resists catalytic hydrogenation. A number of spectroscopic measurements are reported, including unusually small quadrupole splitting effects in the Mössbauer spectra.

show abstract

“…The correlation between the relative affinity of various ligands for N2ase and for some of the synthetic complexes of Fe, Co, Ni, Mo, Ru, Rh, Re, Os, and Ir that bind, but have not yet been shown to reduce, N2 ( Further support for diimide formation in the N2ase system is pro vided by results on the interaction of a nitrogen complex of Re with Mo 4+ (110). A postulated Re=N=N=Mo is formed with a correspond ing large decrease in N-N stretching frequency towards that characteristic of diimide.…”

Section: Figure 12 Nitrogenase Reactions Based On Electron-activatiomentioning

confidence: 96%

The Biochemistry of N₂ Fixation

Hardy

Burns

Parshall

1971

Advances in Chemistry

View full text Add to dashboard Cite

The nature of the N2ase reaction is described with respect to electron donation, energy requirement, and reduction characteristics, with particular analysis of the seven classes of substrates reducible by N2ase, a complex of a Mo-Fe and Fe protein. Chemical and physical characteristics of Fe protein and crystalline Mo-Fe protein are summarized. The two-site mechanism of electron activation and substrate complexation is further developed. Reduction may occur at a biological dinuclear site of Mo and Fe in which N2 is reduced to NH3 via enzyme-bound diimide and hydrazine. Unsolved problems of electron donors, ATP function, H2 evolution and electron donation, substrate reduction, N2ase characteristics and mechanism, and metal roles are tabu lated. Potential utilities of N2 fixation research include in creased protein production and new chemistry of nitrogen.'"phe facile reduction of N2 to NH3 by the natural catalyst, nitrogenase, A is not understood and has never been equalled with synthetic cata lysts. Developments of the past decade may change this. A renaissance in N2 fixation research in both biochemistry and inorganic chemistry is providing the first opportunity for bioinorganic interaction between these previously independent approaches to catalytic N2 reduction. Remark able progress-from crude extracts to crystalline protein and from a single N2ase substrate to recognition of seven classes of substrates-in the elu cidation of the complex biochemistry of N2 fixation has been made during the past decade ( Figure 1) (1,2,3 , 4, 5, 6, 7, 8, 9, 10, 11). Moreover, advances in the inorganic chemistry of N2-fixation-synthesis of transition metal complexes of N2 and reduction of N2 under ambient conditionsare yielding the first examples of bioinorganic models.We will summarize the status of the biochemistry of N2 fixation, including nitrogenase (N2ase) reactions and characteristics, with exten-219

show abstract

Chemical Evidence concerning the Function of Molybdenum in Nitrogenase

Cited by 49 publications

References 4 publications

Catalytic growth of N-doped MgO on Mo(001)

Catalytic growth of N-doped MgO on Mo(001)

Models for the Interaction of Nitrogen with Transition Metals. Part III. Preparation and Properties of some Cationic Arylazo Complexes of Iron

The Biochemistry of N₂ Fixation

Contact Info

Product

Resources

About

Chemical Evidence concerning the Function of Molybdenum in Nitrogenase

Cited by 49 publications

References 4 publications

Catalytic growth of N-doped MgO on Mo(001)

Catalytic growth of N-doped MgO on Mo(001)

Models for the Interaction of Nitrogen with Transition Metals. Part III. Preparation and Properties of some Cationic Arylazo Complexes of Iron

The Biochemistry of N2 Fixation

Contact Info

Product

Resources

About

The Biochemistry of N₂ Fixation