The continuing story of dinitrogen activation

Fryzuk, Michael D.; Johnson, Samuel A.

doi:10.1016/s0010-8545(00)00264-2

Cited by 479 publications

(393 citation statements)

References 114 publications

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“…Although such a transformation is feasible, as evidenced by the biosynthesis of ammonia enabled by nitrogenase enzymes [1][2][3][4], the activation of dinitrogen on transition metal complexes is not trivial and the best man-made homogeneous catalysts for ammonia synthesis can perform only several dozens of catalytic turnovers [5][6][7][8][9][10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Dzik

2016

Inorganics

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Abstract:Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh 3 ) 3 N 2 are presented. We show that in the presence of the title compound, the reaction of N 2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilyl)amine per Co atom in THF (tetrahydrofuran). The aim was to elucidate whether the active catalyst is: (a) the [Co(PPh 3 ) 3 N 2 ]´anion formed after two-electron reduction of the title compound; or (b) a species formed via decomposition of CoH(PPh 3 ) 3 N 2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst.

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Section: Introductionmentioning

confidence: 99%

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Dzik

2016

Inorganics

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“…Apparently, protonation (path 2) of the sulfur donors should be considered as an essential and most promising initial step during the reduction of the dinuclear N 2 complex. [9,10,[16][17][18][19][20][21][22][23][24][25][26][27][28][29] It is the purpose of this study to investigate this first protonation reduction step in order to obtain a microscopic picture of a possible mechanism of a two-electron reduction of protonated Sellmann-type complexes. A detailed understanding of the reaction mechanism should yield suggestions for a particular ligand sphere for sulfur-rich metal complexes designed to stimulate nitrogen activation.…”

Section: Introductionmentioning

confidence: 99%

Car–Parrinello Molecular Dynamics Study of the Initial Dinitrogen Reduction Step in Sellmann‐Type Nitrogenase Model Complexes

Kirchner

Reiher

Hille

et al. 2004

Chemistry A European J

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Car-Parrinello molecular dynamics study of the initial dinitrogen reduction step in Sellmann-type nitrogenase model complexes AbstractWe have studied reduction reactions for nitrogen fixation at Sellmann-type model complexes with Car-Parrinello simulation techniques. These dinuclear complexes are especially designed to emulate the so-called open-side FeMoco model. The main result of this work shows that in order to obtain the reduced species several side reactions have to be suppressed. These involve partial dissociation of the chelate ligands and hydrogen atom transfer to the metal center. Working at low temperature turns out to be one necessary pre-requisite in carrying out successful events. The successful events cannot be described by simple reaction coordinates. Complicated processes are involved during the initiation of the reaction. Our theoretical study emphasizes two experimental strategies which are likely to inhibit the side reactions. Clamping of the two metal fragments by a chelating phosphane ligand should prevent dissociation of the complex. Furthermore, introduction of tert-butyl substituents could improve the solubility and should thus allow usage of a wider range of (mild) acids, reductants, and reaction conditions.

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“…Unfortunately, this problem is still unsolved. While much has been learned about how to synthesize dinitrogen complexes (hundreds are now known) (3)(4)(5)(6)(7) and how N 2 binds to one or more metal complexes (7)(8)(9), there are only a few reports of homogeneous systems that involve turnover of molecular nitrogen, and these systems are not efficient or broadly applicable (10,11).…”

mentioning

confidence: 99%

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

Spencer

Patrick²,

Fryzuk³

2006

Proc. Natl. Acad. Sci. U.S.A.

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The continuing story of dinitrogen activation

Cited by 479 publications

References 114 publications

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Car–Parrinello Molecular Dynamics Study of the Initial Dinitrogen Reduction Step in Sellmann‐Type Nitrogenase Model Complexes

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

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