Dinitrogen Coordination Chemistry:  On the Biomimetic Borderlands

MacKay, Bruce A.; Fryzuk, Michael D.

doi:10.1021/cr020610c

Cited by 633 publications

(465 citation statements)

References 172 publications

(250 reference statements)

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“…to the Fe atom in the catalyst), Me 3 SiCl (600 equiv. to the Fe atom in the catalyst) and [Fe(CO) 5 ] in tetrahydrofuran (THF) (40 ml) was stirred at room temperature for 20 h under 1 atm of N 2 . After the reaction, 1 (25 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…Separately, we confirmed that no formation of 1 was observed in the absence of Time profile of iron-catalysed reaction of N 2 into N(SiMe 3 ) 3 . In order to obtain more information on the reaction pathway, the relationship between the reaction time and the yields of 1 was investigated in the reaction of N 2 (1 atm) with Na and Me 3 SiCl in the presence of a catalytic amount of [Fe(CO) 5 ] in THF at room temperature. The time profile is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…This result apparently indicates that the catalytic active species is a homogeneous Fe complex. Second, the experimental result that both [Fe(CO) 5 ] and ferrocenes have almost the same catalytic activity towards the formation of 1 suggests that common Fe complexes, generated in situ from Na, Me 3 Fig. 2 adopt a slightly deformed tetrahedral structure.…”

Section: Discussionmentioning

confidence: 98%

“…Industrially, NH 3 is produced from N 2 and H 2 using Fe-based heterogeneous catalysts under harsh reaction conditions, where enormous energy is also necessary for the production of H 2 from fossil fuels such as natural gas 1 . Although the stoichiometric transformation using transition metal-N 2 complexes has been well investigated towards the goal of nitrogen fixation under mild reaction conditions [2][3][4] , only a few examples of the catalytic transformation of N 2 using transition metal-N 2 complexes 5,6 as catalysts have been reported [7][8][9] . In fact, only two types of Mo-N 2 complexes bearing triamidoamine 7 ligand and 2,6-bis(di-tert-butylphosphinomethyl)pyridine 9 ligand, respectively, worked as effective catalysts to promote the direct conversion of N 2 into NH 3 under ambient reaction conditions.…”

mentioning

confidence: 99%

“…of 1 was produced based on the catalyst. In this reaction system, simple and commercially available Fe complexes such as [Fe(CO) 5 ] and ferrocenes have been found to work as effective catalysts. This is the first successful example of the Fe-catalysed conversion of N 2 under ambient conditions.…”

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Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

et al. 2012

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 98%

mentioning

confidence: 99%

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confidence: 99%

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Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

et al. 2012

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Nitrogenase: Metal Cluster Models

Barri��re¹

2005

Encyclopedia of Inorganic Chemistry

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This article reviews the synthesis and properties of inorganic clusters that model the iron–sulfur centers found in the nitrogenase enzyme. These sites are of the Fe 4 S 4 , Fe 8 S 7 , and MoFe 7 S 9 stoichiometry. The enzyme [Fe 4 S 4 ] 2+/1+ center is well modeled by synthetic clusters bearing thiolate ligands at iron. However, the [Fe 4 S 4 ] 0 state is stabilized in the enzyme and has not been reproduced in the laboratory so far. Recent progress in synthetic models of the Fe 8 S 7 P‐cluster is reported. One of its known structures can be obtained by self‐assembly from basic constituents, or synthesized in a stepwise fashion from smaller clusters yielding topological analogues. The most challenging cluster to model is the FeMo‐cofactor. This MoFe 7 S 9 center is the site of dinitrogen reduction to ammonia. The cluster also exists with vanadium or iron in place of molybdenum in alternative nitrogenases. It was shown only recently that the FeMo‐cofactor is centered on a light atom that is probably a nitrogen atom. Structural modeling of this center is limited. Only its molybdenum or heterometal end has been accurately modeled. Functional chemistry of good structural models, those with sulfur ligands and metal–metal bonds, only concerns the reduction of already partially reduced diazo substrates such as diazene or hydrazine.

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Ammonia Synthesis—Homogeneous

Shibata

Seino

Mizobe

et al. 2010

Encyclopedia of Catalysis

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Chemical N 2 reducing systems to ammonia promoted by the transition metal complexes in solutions have been surveyed. This review includes the ammonia formation facilitated not only by the active transition metal species generated in situ but, more importantly, by the well‐defined N 2 complexes. The latter provides the important information about the mechanism for the chemical and biological nitrogen fixation and the clue to the development of new effective catalyst for N 2 reduction.

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Dinitrogen Coordination Chemistry: On the Biomimetic Borderlands

Cited by 633 publications

References 172 publications

Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

Nitrogenase: Metal Cluster Models

Ammonia Synthesis—Homogeneous

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