Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Crossland, Justin L.; Tyler, David R.

doi:10.1016/j.ccr.2010.01.005

Cited by 224 publications

(223 citation statements)

References 124 publications

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“…In this reaction system, up to 34 equiv. of N(SiMe 3 ) 3 Recently, the preparation of Fe-N 2 complexes and their stoichiometric reactivity have been intensively studied [24][25][26][27] , but the Fe-catalysed transformation of N 2 by using Fe-N 2 complexes has not yet been reported until now 28 . We believe that the results described here provide valuable and useful information to develop the Fe-catalysed transformation of N 2 .…”

Section: Discussionmentioning

confidence: 99%

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

et al. 2012

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Section: Discussionmentioning

confidence: 99%

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

et al. 2012

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“…In this context, most of the effort has been focused on molybdenum and iron systems [14][15][16][17][18]. Two major strategies for catalytic N2 activation by homogeneous systems were developed: reductive protonation to yield ammonia and reductive silylation to yield silylamines ( Figure 1).…”

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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“…Although the site(s) of N 2 reduction remain(s) uncertain, a body of evidence that includes biochemical, spectroscopic, and computational studies on FeMoco point to a belt Fe center as a plausible candidate (2,(9)(10)(11)(12)(13). In a scenario in which N 2 binds terminally to one of the belt Fe centers, the N 2 ligand would initially be coordinated trans to the interstitial C atom ( Fig.…”

mentioning

confidence: 99%

Fe–N ₂ /CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco)

Rittle

Peters

2013

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

131

151

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We report here a series of four-and five-coordinate Fe model complexes that feature an axial tri(silyl)methyl ligand positioned trans to a substrate-binding site. This arrangement is used to crudely model a single-belt Fe site of the FeMo-cofactor that might bind N 2 at a position trans to the interstitial C atom. Reduction of a trigonal pyramidal Fe(I) complex leads to uptake of N 2 and subsequent functionalization furnishes an open-shell Fe-diazenido complex. A related series of five-coordinate Fe-CO complexes stable across three redox states is also described. Spectroscopic, crystallographic, and Density Functional Theory (DFT) studies of these complexes suggest that a decrease in the covalency of the Fe-C alkyl interaction occurs upon reduction and substrate binding. This leads to unusually long Fe-C alkyl bond distances that reflect an ionic Fe-C bond. The data presented are contextualized in support of a hypothesis wherein modulation of a belt Fe-C interaction in the FeMo-cofactor facilitates substrate binding and reduction.nitrogenase | nitrogen fixation | Fe-N 2 complexes | small molecule activation | ammonia production

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Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Cited by 224 publications

References 124 publications

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

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

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

Fe–N ₂ /CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco)

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Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Cited by 224 publications

References 124 publications

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

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

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

Fe–N 2 /CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco)

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Fe–N ₂ /CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco)