Catalytic Reduction of Hydrazine to Ammonia by a Mononuclear Iron(II) Complex on a Tris(thiolato)phosphine Platform

Chang, Ya Ho; Chan, Pooi Mun; Tsai, Yi Fang; Lee, Gene Hsiang; Hsu, Hua Fen

doi:10.1021/ic402108w

Cited by 29 publications

(21 citation statements)

References 37 publications

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“…The formation of both ammonia and hydrazine is in sharp contrast to that in the Peters' reaction systems 19 20 21 22 , where no formation of hydrazine was observed at all when iron-dinitrogen complexes bearing triphosphine-borane and -alkyl ligands, and two cyclic carbene ligands were used as catalysts. Separately, we confirmed that the partial reduction 7 44 45 46 47 of hydrazine into ammonia in the presence of a catalytic amount of 4 proceeded in Et 2 O at −78 °C for 1 h ( Supplementary Table 6 ). However, the use of THF in place of Et 2 O relatively inhibited the partial reduction of hydrazine into ammonia under the same reaction conditions.…”

Section: Resultssupporting

confidence: 66%

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

et al. 2016

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Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase.

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Section: Resultssupporting

confidence: 66%

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

et al. 2016

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“…Additionally, none of these S-based systems has been reported to perform N 2 reduction, though some are capable of catalytic reduction of hydrazine. 200,201 …”

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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“…Accordingly, we observed the additional formation of yellow needles of 3a in the synthesis of 1 upon longer crystallization times when carried out with aliquots of P n Bu 3 in thf/Et 2 O. We note that there are only three examples of iron complexes in the CSD comprising NH 3 together with a sulfur based ligand (sulfide or thiolate) namely [(LFeNH 3 ) 2 (µ‐S)] (L = {HC(CMeN(2,6‐diisopropylphenyl)) 2 } – ), [N(Et) 4 ][Fe(PS 3 '')(NH 3 )] (PS 3 '' = P(C 6 H 3– 3‐Me 3 Si‐2‐S) 3 3– ) and [Fe(NH 3 )(‘N H S 4 ')] (‘N H S 4 ' 2– = HN(C 2 H 4 SC 6 H 4– 2‐S) 2 2– ) …”

Section: Resultsmentioning

confidence: 82%

1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of _∞¹[Fe(SR)₂] (R = Ph, Mes), _∞¹[Fe(NH₃)(SPh)(µ‐SPh)] and _∞¹[(µ‐SPh)Fe(NH₃)₂(µ‐SPh)₂Fe(µ‐SPh)]

Eichhöfer

Buth

2019

Eur J Inorg Chem

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The first examples of polymeric homoleptic iron(II) thiolato complexes ∞ 1 [Fe(SPh) 2 ] and ∞ 1 [Fe(SMes) 2 ] (Ph = phenyl = C 6 H 5 , Mes = mesityl = C 6 H 2-2,4,6-(CH 3 ) 3 ) have been both prepared by reaction of [{Fe(N(SiMe 3 ) 2 ) 2 } 2 ] with four equivalents of HSR ( R = Ph, Mes). In the crystal the two compounds form onedimensional chains with bridging thiolato ligands comprising distinctly different Fe-S-Fe bridging angles namely 75.20-75.25°in ∞ 1 [Fe(SPh) 2 ] and 91.38°in ∞ 1 [Fe(SMes) 2 ]. Reaction of ∞ 1 [Fe(SPh) 2 ] with stoichiometric amounts of NH 3 , generated by reaction of HN(SiMe 3 ) 2 with CH 3 OH, resulted in the formation [a]

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Catalytic Reduction of Hydrazine to Ammonia by a Mononuclear Iron(II) Complex on a Tris(thiolato)phosphine Platform

Cited by 29 publications

References 37 publications

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

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

1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of _∞¹[Fe(SR)₂] (R = Ph, Mes), _∞¹[Fe(NH₃)(SPh)(µ‐SPh)] and _∞¹[(µ‐SPh)Fe(NH₃)₂(µ‐SPh)₂Fe(µ‐SPh)]

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Catalytic Reduction of Hydrazine to Ammonia by a Mononuclear Iron(II) Complex on a Tris(thiolato)phosphine Platform

Cited by 29 publications

References 37 publications

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

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

1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of ∞1[Fe(SR)2] (R = Ph, Mes), ∞1[Fe(NH3)(SPh)(µ‐SPh)] and ∞1[(µ‐SPh)Fe(NH3)2(µ‐SPh)2Fe(µ‐SPh)]

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1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of _∞¹[Fe(SR)₂] (R = Ph, Mes), _∞¹[Fe(NH₃)(SPh)(µ‐SPh)] and _∞¹[(µ‐SPh)Fe(NH₃)₂(µ‐SPh)₂Fe(µ‐SPh)]