Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia.

ABSTRACT: It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle.

SUBMITTER: Tanaka H

PROVIDER: S-EPMC4015321 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia.

Tanaka Hiromasa H Arashiba Kazuya K Kuriyama Shogo S Sasada Akira A Nakajima Kazunari K Yoshizawa Kazunari K Nishibayashi Yoshiaki Y

Nature communications 20140428

It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calcul ...[more]

PMID: 24769530

Similar Datasets

Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation.

Project description:Intensive efforts for the transformation of dinitrogen using transition metal-dinitrogen complexes as catalysts under mild reaction conditions have been made. However, limited systems have succeeded in the catalytic formation of ammonia. Here we show that newly designed and prepared dinitrogen-bridged dimolybdenum complexes bearing N-heterocyclic carbene- and phosphine-based PCP-pincer ligands [{Mo(N2)2(PCP)}2(μ-N2)] (1) work as so far the most effective catalysts towards the formation of ammonia from dinitrogen under ambient reaction conditions, where up to 230 equiv. of ammonia are produced based on the catalyst. DFT calculations on 1 reveal that the PCP-pincer ligand serves as not only a strong σ-donor but also a π-acceptor. These electronic properties are responsible for a solid connection between the molybdenum centre and the pincer ligand, leading to the enhanced catalytic activity for nitrogen fixation.

| S-EPMC5382288 | biostudies-literature

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

Project description: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.

| S-EPMC4961768 | biostudies-literature

Nitrogen fixation catalyzed by ferrocene-substituted dinitrogen-bridged dimolybdenum-dinitrogen complexes: unique behavior of ferrocene moiety as redox active site.

Project description:A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing metallocene-substituted PNP-pincer ligands is synthesized by the reduction of the corresponding monomeric molybdenum-trichloride complexes under 1 atm of molecular dinitrogen. Introduction of ferrocene as a redox-active moiety to the pyridine ring of the PNP-pincer ligand increases the catalytic activity for the formation of ammonia from molecular dinitrogen, up to 45 equiv. of ammonia being formed based on the catalyst (22 equiv. of ammonia based on each molybdenum atom of the catalyst). The time profile for the catalytic reaction reveals that the presence of the ferrocene unit in the catalyst increases the rate of ammonia formation. Electrochemical measurement and theoretical studies indicate that an interaction between the Fe atom of the ferrocene moiety and the Mo atom in the catalyst may play an important role to achieve a high catalytic activity.

| S-EPMC5707465 | biostudies-literature

Catalytic Dinitrogen Reduction to Ammonia at a Triamidoamine-Titanium Complex.

Project description:Catalytic reduction of N2 to NH3 by a Ti complex has been achieved, thus now adding an early d-block metal to the small group of mid- and late-d-block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH3 by N2 reduction and protonolysis under homogeneous, abiological conditions. Reduction of [TiIV (TrenTMS )X] (X=Cl, 1A; I, 1B; TrenTMS =N(CH2 CH2 NSiMe3 )3 ) with KC8 affords [TiIII (TrenTMS )] (2). Addition of N2 affords [{(TrenTMS )TiIII }2 (μ-η1 :η1 -N2 )] (3); further reduction with KC8 gives [{(TrenTMS )TiIV }2 (μ-η1 :η1 :η2 :η2 -N2 K2 )] (4). Addition of benzo-15-crown-5 ether (B15C5) to 4 affords [{(TrenTMS )TiIV }2 (μ-η1 :η1 -N2 )][K(B15C5)2 ]2 (5). Complexes 3-5 treated under N2 with KC8 and [R3 PH][I], (the weakest H+ source yet used in N2 reduction) produce up to 18 equiv of NH3 with only trace N2 H4 . When only acid is present, N2 H4 is the dominant product, suggesting successive protonation produces [{(TrenTMS )TiIV }2 (μ-η1 :η1 -N2 H4 )][I]2 , and that extruded N2 H4 reacts further with [R3 PH][I]/KC8 to form NH3 .

| S-EPMC6003280 | biostudies-literature

Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand.

Project description:Dinitrogen is an abundant and promising material for valuable organonitrogen compounds containing carbon-nitrogen bonds. Direct synthetic methods for preparing organonitrogen compounds from dinitrogen as a starting reagent under mild reaction conditions give insight into the sustainable production of valuable organonitrogen compounds with reduced fossil fuel consumption. Here we report the catalytic reaction for the formation of cyanate anion (NCO-) from dinitrogen under ambient reaction conditions. A molybdenum-carbamate complex bearing a pyridine-based 2,6-bis(di-tert-butylphosphinomethyl)pyridine (PNP)-pincer ligand is synthesized from the reaction of a molybdenum-nitride complex with phenyl chloroformate. The conversion between the molybdenum-carbamate complex and the molybdenum-nitride complex under ambient reaction conditions is achieved. The use of samarium diiodide (SmI2) as a reductant promotes the formation of NCO- from the molybdenum-carbamate complex as a key step. As a result, we demonstrate a synthetic cycle for NCO- from dinitrogen mediated by the molybdenum-PNP complexes in two steps. Based on this synthetic cycle, we achieve the catalytic synthesis of NCO- from dinitrogen under ambient reaction conditions.

| S-EPMC9592615 | biostudies-literature

Catalytic reduction of dinitrogen to ammonia at a single molybdenum center.

Project description:Since our discovery of the catalytic reduction of dinitrogen to ammonia at a single molybdenum center, we have embarked on a variety of studies designed to further understand this complex reaction cycle. These include studies of both individual reaction steps and of ligand variations. An important step in the reaction sequence is exchange of ammonia for dinitrogen in neutral molybdenum(III) compounds. We have found that this exchange reaction is first order in dinitrogen and relatively fast (complete in <1 h) at 1 atm of dinitrogen. Variations of the terphenyl substituents in the triamidoamine ligand demonstrate that the original ligand is not unique in its ability to yield successful catalysts. However, complexes that contain sterically less demanding ligands fail to catalyze formation of ammonia from dinitrogen; it is proposed as a consequence of a base-catalyzed decomposition of a diazenido (Mo-N=NH) intermediate.

| S-EPMC1693870 | biostudies-literature

(Electro-)chemical Splitting of Dinitrogen with a Rhenium Pincer Complex.

Project description:The splitting of N2 into well-defined terminal nitride complexes is a key reaction for nitrogen fixation at ambient conditions. In continuation of our previous work on rhenium pincer mediated N2 splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl2(L2)] {L2 = N(CHCHPtBu2)2 -} is reported. The electrochemical characterization of [ReCl2(L2)] and comparison with our previously reported platform [ReCl2(L1)] {L1 = N(CH2CH2PtBu2)2 -} provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N2 derived nitride complex [Re(N)Cl(L2)] with electrophiles is presented.

| S-EPMC7217231 | biostudies-literature

Nature's nitrite-to-ammonia expressway, with no stop at dinitrogen.

Project description:Since the characterization of cytochrome c552 as a multiheme nitrite reductase, research on this enzyme has gained major interest. Today, it is known as pentaheme cytochrome c nitrite reductase (NrfA). Part of the NH4+ produced from NO2- is released as NH3 leading to nitrogen loss, similar to denitrification which generates NO, N2O, and N2. NH4+ can also be used for assimilatory purposes, thus NrfA contributes to nitrogen retention. It catalyses the six-electron reduction of NO2- to NH4+, hosting four His/His ligated c-type hemes for electron transfer and one structurally differentiated active site heme. Catalysis occurs at the distal side of a Fe(III) heme c proximally coordinated by lysine of a unique CXXCK motif (Sulfurospirillum deleyianum, Wolinella succinogenes) or, presumably, by the canonical histidine in Campylobacter jejeuni. Replacement of Lys by His in NrfA of W. succinogenes led to a significant loss of enzyme activity. NrfA forms homodimers as shown by high resolution X-ray crystallography, and there exist at least two distinct electron transfer systems to the enzyme. In γ-proteobacteria (Escherichia coli) NrfA is linked to the menaquinol pool in the cytoplasmic membrane through a pentaheme electron carrier (NrfB), in δ- and ε-proteobacteria (S. deleyianum, W. succinogenes), the NrfA dimer interacts with a tetraheme cytochrome c (NrfH). Both form a membrane-associated respiratory complex on the extracellular side of the cytoplasmic membrane to optimize electron transfer efficiency. This minireview traces important steps in understanding the nature of pentaheme cytochrome c nitrite reductases, and discusses their structural and functional features.

| S-EPMC8840924 | biostudies-literature

Synthesis of diamidopyrrolyl molybdenum complexes relevant to reduction of dinitrogen to ammonia.

Project description:A potentially useful trianionic ligand for the reduction of dinitrogen catalytically by molybdenum complexes is one in which one of the arms in a [(RNCH(2)CH(2))(3)N](3-) ligand is replaced by a 2-mesitylpyrrolyl-alpha-methyl arm, that is, [(RNCH(2)CH(2))(2)NCH(2)(2-MesitylPyrrolyl)](3-) (R = C(6)F(5), 3,5-Me(2)C(6)H(3), or 3,5-t-Bu(2)C(6)H(3)). Compounds have been prepared that contain the ligand in which R = C(6)F(5) ([C(6)F(5)N)(2)Pyr](3-)); they include [(C(6)F(5)N)(2)Pyr]Mo(NMe(2)), [(C(6)F(5)N)(2)Pyr]MoCl, [(C(6)F(5)N)(2)Pyr]MoOTf, and [(C(6)F(5)N)(2)Pyr]MoN. Compounds that contain the ligand in which R = 3,5-t-Bu(2)C(6)H(3) ([Ar(t-Bu)N)(2)Pyr](3-)) include {[(Ar(t-Bu)N)(2)Pyr]Mo(N(2))}Na(15-crown-5), {[(Ar(t-Bu)N)(2)Pyr]Mo(N(2))}[NBu(4)], [(Ar(t-Bu)N)(2)Pyr]Mo(N(2)) (nu(NN) = 2012 cm(-1) in C(6)D(6)), {[(Ar(t-Bu)N)(2)Pyr]Mo(NH(3))}BPh(4), and [(Ar(t-Bu)N)(2)Pyr]Mo(CO). X-ray studies are reported for [(C(6)F(5)N)(2)Pyr]Mo(NMe(2)), [(C(6)F(5)N)(2)Pyr]MoCl, and [(Ar(t-Bu)N)(2)Pyr]MoN. The [(Ar(t-Bu)N)(2)Pyr]Mo(N(2))(0/-) reversible couple is found at -1.96 V (in PhF versus Cp(2)Fe(+/0)), but the [(Ar(t-Bu)N)(2)Pyr]Mo(N(2))(+/0) couple is irreversible. Reduction of {[(Ar(t-Bu)N)(2)Pyr]Mo(NH(3))}BPh(4) under Ar at approximately -1.68 V at a scan rate of 900 mV/s is not reversible. Ammonia in [(Ar(t-Bu)N)(2)Pyr]Mo(NH(3)) can be substituted for dinitrogen in about 2 h if 10 equiv of BPh(3) are present to trap the ammonia that is released. [(Ar(t-Bu)N)(2)Pyr]Mo-N=NH is a key intermediate in the proposed catalytic reduction of dinitrogen that could not be prepared. Dinitrogen exchange studies in [(Ar(t-Bu)N)(2)Pyr]Mo(N(2)) suggest that steric hindrance by the ligand may be insufficient to protect decomposition of [(Ar(t-Bu)N)(2)Pyr]Mo-N=NH through a variety of pathways. Three attempts to reduce dinitrogen catalytically with [(Ar(t-Bu)N)(2)Pyr]Mo(N) as a "catalyst" yielded an average of 1.02 +/- 0.12 equiv of NH(3).

| S-EPMC2931342 | biostudies-literature

Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia.

Project description:A nitrogenase-inspired biomimetic chalcogel system comprising double-cubane [Mo2Fe6S8(SPh)3] and single-cubane (Fe4S4) biomimetic clusters demonstrates photocatalytic N2 fixation and conversion to NH3 in ambient temperature and pressure conditions. Replacing the Fe4S4 clusters in this system with other inert ions such as Sb(3+), Sn(4+), Zn(2+) also gave chalcogels that were photocatalytically active. Finally, molybdenum-free chalcogels containing only Fe4S4 clusters are also capable of accomplishing the N2 fixation reaction with even higher efficiency than their Mo2Fe6S8(SPh)3-containing counterparts. Our results suggest that redox-active iron-sulfide-containing materials can activate the N2 molecule upon visible light excitation, which can be reduced all of the way to NH3 using protons and sacrificial electrons in aqueous solution. Evidently, whereas the Mo2Fe6S8(SPh)3 is capable of N2 fixation, Mo itself is not necessary to carry out this process. The initial binding of N2 with chalcogels under illumination was observed with in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS). (15)N2 isotope experiments confirm that the generated NH3 derives from N2 Density functional theory (DFT) electronic structure calculations suggest that the N2 binding is thermodynamically favorable only with the highly reduced active clusters. The results reported herein contribute to ongoing efforts of mimicking nitrogenase in fixing nitrogen and point to a promising path in developing catalysts for the reduction of N2 under ambient conditions.

| S-EPMC4878479 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data