N<sub>2</sub> Functionalization at Iron Metallaboratranes

Moret, Marc‐Etienne; Peters, Jonas C.

doi:10.1021/ja208675p

Cited by 187 publications

(178 citation statements)

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“…Though there are no examples of iron species that are coordinated by the parent diazenido ligand (Fe-N 2 H), complexes of the type Fe(η 1 -N 2 R) can be accessed via alkylation or silylation of a precursor dinitrogen complex Fe(η 1 -N 2 R), 9g,33 or by deprotonation of a hydrazine species Fe(η 1 -N 2 H 3 Ph) (with concomitant H 2 release). 6d It is anticipated that hydrazido oxidation may be a viable synthetic route to diazenido species, by analogy to hydrazine oxidation to give diazene species.…”

Section: Resultsmentioning

confidence: 99%

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Saouma

Peters

2012

Inorg. Chem.

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This article describes the synthesis and characterization of several low-spin iron(II) complexes that coordinate hydrazine (N2H4), hydrazido (N2H3−), and ammonia. The sterically encumbered tris(di-meta-terphenylphosphino)borate ligand, [PhBPmter3]−, is introduced to provide access to species that cannot be stabilized with the [PhBPPh3]− ligand ([PhBPR3]− = PhB(CH2PR2)3−). Treatment of [PhBPmter3]FeMe with hydrazine generates the unusual 5-coordinate hydrazido complex [PhBPmter3]Fe(η2-N2H3) (1), in which the hydrazido serves as an L2X-type ligand. Upon coordination of an L-type ligand, the hydrazido shifts to an LX-type ligand, generating [PhBPmter3]Fe(L)(η2-N2H3) (L = N2H4 (2) or NH3 (3)). In contrast, treatment of [PhBPPh3]FeMe with hydrazine forms the adduct [PhBPPh3]Fe(Me)(η2-N2H4) (5). Complex 5 is thermally unstable to methane loss, generating intermediate [PhBPPh3]Fe(η2-N2H3), which undergoes bimolecular coupling to produce {[PhBPPh3]Fe}2(µ-η1:η1-N2H4)(µ-η2:η2-N2H2). The oxidation of these and related hydrazine and hydrazido species is also presented. For example, oxidation of 1 or 5 with Pb(OAc)4 results in disproportionation of the N2Hx ligand (x = 3, 4), and formation of [PhBPR3]Fe(NH3)(OAc) (R = Ph (9) and mter (11)).

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Section: Resultsmentioning

confidence: 99%

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Saouma

Peters

2012

Inorg. Chem.

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“…17). 61,157,191,192,41,44,165 Peters has shown that phosphine ligands provide excellent platforms for functionalization of N 2 on iron, 60,193,194 and enable characterization of potential N 2 reduction intermediates Fe-N x H y , 98,99,165,194–196 including systems that feature a coordinated hydride. 40,42,43 Ammonia production by tripodal trisphosphine ligands with an axial donor (Si, C, or B) increases in the order Si < C < B.…”

Section: Fe-nxhy Complexes With Sulfur Ligandsmentioning

confidence: 99%

Insight into the Iron–Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands

2016

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Nitrogenase enzymes are used by microorganisms for converting atmospheric N2 to ammonia, which provides an essential source of N atoms for higher organisms. The active site of the molybdenum-dependent nitrogenase is the unique carbide-containing iron-sulfur cluster called the iron-molybdenum cofactor (FeMoco). On the FeMoco, N2 binding is suggested to occur at one or more iron atoms, but the structures of the catalytic intermediates are not clear. In order to establish the feasibility of different potential mechanistic steps during biological N2 reduction, chemists have prepared iron complexes that mimic various structural aspects of the iron sites in FeMoco. This reductionist approach gives mechanistic insight, and also uncovers fundamental principles that could be used more broadly for small molecule activation. Here, we review recent results and highlight directions for future research. In one direction, synthetic iron complexes have now been shown to bind N2, break the N-N triple bond, and produce ammonia catalytically. Carbon and sulfur based donors have been incorporated into the ligand spheres of Fe-N2 complexes to show how these atoms may influence the structure and reactivity of the FeMoco. Hydrides have been incorporated into synthetic systems, which can bind N2, reduce some nitrogenase substrates, and/or reductively eliminate H2 to generate reduced iron centers. Though some carbide-containing iron clusters are known, none yet have sulfide bridges or high-spin iron atoms like the FeMoco.

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“…[77] An important feature of the (TP iPr B)Fe system {TP iPr B = tris[2-(diisopropylphosphanyl)-phenyl]borane}, is the presence of a flexible Fe-B interaction. [78,79] The four-coordinate iron complex [37] The catalytic activity is slightly lower than the activities of Mo catalysts (8.5 equiv. NH 3 per Fe equiv.…”

Section: Ch]mentioning

confidence: 99%

Late Metal Scaffolds that Activate Both, Dinitrogen and Reduced Dinitrogen Species N_xH_y

Köthe

Limberg

2014

Zeitschrift anorg allge chemie

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Abstract. In the context of biological nitrogen fixation, the question whether molybdenum or iron is the site for substrate binding and reduction is still discussed controversially. Therefore, the development of relevant model compounds containing early or late transition metals is essential in understanding the nature and behavior of intermediates bound to the FeMo-cofactor. Ligated early transition metal atoms are known to strongly activate N 2 and mediate its cleavage, but the resulting complexes contain metal-nitrogen bonds, which often elude

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N₂ Functionalization at Iron Metallaboratranes

Cited by 187 publications

References 41 publications

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Insight into the Iron–Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands

Late Metal Scaffolds that Activate Both, Dinitrogen and Reduced Dinitrogen Species N_xH_y

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N2 Functionalization at Iron Metallaboratranes

Cited by 187 publications

References 41 publications

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species

Insight into the Iron–Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands

Late Metal Scaffolds that Activate Both, Dinitrogen and Reduced Dinitrogen Species NxHy

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N₂ Functionalization at Iron Metallaboratranes

Late Metal Scaffolds that Activate Both, Dinitrogen and Reduced Dinitrogen Species N_xH_y