Dinitrogen Reduction and Functionalization by a Siloxide Supported Thulium-Potassium Complex for the formation of Ammonia or Hydrazine Derivatives.

The dinitrogen (N2) chemistry of lanthanides remains less developed compared to the d-block metals and lanthanide-promoted N2 functionalization chemistry in well-defined lanthanide complexes remains elusive. Here we report the synthesis and characterization (SQUID, EPR, DFT, X-Ray) of the siloxide supported heterobimetallic (Tm/K) complexes [{KTm(OSi(OtBu)3)3}2(µ-η2:η2-N2)] (1) and [K3{Tm(OSi(OtBu)3)3}2(µ-η2:η2-N2)] (2). Complex 2 provides a rare example of a metal complex of the triply reduced N23- radical. The structure of 2 differs from the few previously reported N23- complexes as it presents two Tm and three K cations binding the N23- radical, facilitating N2 functionalization. Notably, the K3Tm2-bound N23- moiety reacts with excess H+ to form NH4Cl in 18% yield, and with MeOTf at room temperature to yield the dimethyl hydrazido complex [K2{Tm(OSi(OtBu)3)3}2(µ-(CH3)NN(CH3))] (3). Protonolysis of 3yields MeHN-NMeH·2HCl in 18 % yield.

Experimental Observation of a Terminal Borylene-Dinitrogen Adduct via Cleavage of a 1,2,3,4,5-Diboratriazoline.

While azides do not react with simple alkenes except under harsh conditions, a diboron alkene analogue, the doubly cyclic alkyl(amino)carbene (CAAC)-stabilized dicyanodiborene 1, reacts spontaneously with organic azides (7-10 equiv.) at room temperature to yield two equivalents of stable CAAC-stabilized imino(cyano)boranes (2-R). NMR-spectroscopic monitoring of the reaction mixtures shows the initial formation of a 1:1 mixture of 2-R and a relatively long-lived intermediate (Int), which in the presence of excess azide is converted into a second equivalent of 2-R. In the absence of excess azide, however, Int decomposes to 3, the product of an intramolecular C‒H activation by a putative dicoordinate borylene intermediate "(CAAC)B(CN)". Mechanistic insights from trapping experiments, NMR-spectroscopic and high-resolution mass spectrometry data, as well as DFT computations reveal that Int is the terminal borylene end-on-dinitrogen adduct [(CAAC)B(CN)(η1-N2)]. The formation of the iminoboranes 2-R from diborene 1 and RN3 proceeds via an azide-diborene Huisgen-type [3+2] cycloaddition reaction, followed by a retro-[3+2] cycloaddition, yielding 2-R and [(CAAC)B(CN)(η1-N2)]. The latter then undergoes either N2 extrusion and intramolecular C‒H activationto generate 3, or a Staudinger-type reaction with a second equivalent of azide to generate a second equivalent of the iminoborane 2-R.

N2 as an Efficient IR Probe Molecule for the Investigation of Ceria-Containing Materials.

Ceria and ceria-based catalysts are very important in redox and acid-base catalysis. Nanoceria have also been found to be important in biomedical applications. To design efficient materials, it is necessary to thoroughly understand the surface chemistry of ceria, and one of the techniques that provides such information about the surface is the vibrational spectroscopy of probe molecules. Although the most commonly used probe is CO, it has some disadvantages when applied to ceria and ceria-based catalysts. CO can easily reduce the material, forming carbonate-like species, and can be disproportionate, thus modifying the surface. Here, we offer a pioneering study of the adsorption of 15N2 at 100 K, demonstrating that dinitrogen can be more advantageous than CO when studying ceria-based materials. As an inert gas, N2 is not able to oxidize or reduce cerium cations and does not form any surface anionic species able to modify the surface. It is infrared and transparent, and thus there is no need to subtract the gas phase spectrum, something that often increases the noise level. Being a weaker base than CO, N2 has a negligible induction effect. By using stoichiometric nano-shaped ceria samples, we concluded that 15N2 can distinguish between surface Ce4+ sites on different, low index planes; with cations on the {110} facets and on some of the edges, Ce4+-15N2 species with IR bands at 2258-2257 cm-1 are formed. Bridging species, where one of the N atoms from the molecule interacts with two Ce4+ cations, are formed on the {100} facets (2253-2252 cm-1), while the interaction with the {111} facets is very weak and does not lead to the formation of measurable amounts of complexes. All species are formed by electrostatic interaction and disappear during evacuation at 100 K. In addition, N2 provides more accurate information than CO on the acidity of the different OH groups because it does not change the binding mode of the hydroxyls.

Plants mitigate ecosystem nitrous oxide emissions primarily through reductions in soil nitrate content: Evidence from a meta-analysis.

Nitrous oxide (N2O) is a potent greenhouse gas (GHG) and an ozone-depleting substance. The presence of plants in an ecosystem can either increase or decrease N2O emissions, or play a negligible role in driving N2O emissions. Here, we conducted a meta-analysis comparing ecosystem N2O emissions from planted and unplanted systems to evaluate how plant presence influences N2O emissions and examined the mechanisms driving observed responses. Our results indicate that plant presence reduces N2O emissions while it increases dinitrogen (N2) emissions from ecosystems through decreases in soil nitrate concentration as well as increases in complete denitrification and mineral N immobilization. The response of N2O emissions to plant presence was universal across major terrestrial ecosystems - including forests, grassland and cropland - and it did not vary with N fertilization. Further, in light of the potential mechanisms of N2O formation in plant cells, we discussed how plant presence could enhance the emission of N2O from plants themselves. Improving our understanding of the mechanisms driving N2O emissions in response to plant presence could be beneficial for enhancing the robustness for predictions of our GHG sinks and sources and for developing strategies to minimize emissions at the ecosystem scale.

Oxidation of Ammonia Catalyzed by a Molecular Iron Complex: Translating Chemical Catalysis to Mediated Electrocatalysis.

Ammonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon-neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth-abundant transition metal complex, trans-[LFeII(MeCN)2][PF6]2, where L is a macrocyclic ligand bearing four N-heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N2 per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator (p-MeOC6H4)3N exhibited a catalytic half-wave potential (Ecat/2) of 0.18 V vs [Cp2Fe]+/0 in MeCN, and achieved 9.3 turnovers of N2 at an applied potential of 0.20 V vs [Cp2Fe]+/0 at -20 °C in controlled-potential electrolysis, with a Faradaic efficiency of 75 %. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFeIV(NH2)2]2+, and thereafter bimetallic coupling to form an N-N bond.

Seven-Coordinate Group 6 Metal Hydrides Obtained by H2 Activation at B(C6F5)3 Adducts of N2 Complexes: Frustrated Lewis Pair-Type Reactivity of The B-N Linkage.

The adducts 2M,R of general formula trans-[(L)M{R2P(CH2)2PR2}2{N2B(C6F5)3}] (L=ø or N2, M=Mo or W, R=Et or Ph), formed from Lewis acid-base pairing of B(C6F5)3 to a dinitrogen ligand of zero-valent group 6 bis(phosphine) complexes trans-[M{R2P(CH2)2PR2}2(N2)2] are shown to react with dihydrogen to afford hepta-coordinated bis(hydride) complexes [M(H)2{R2P(CH2)2PR2}{N2B(C6F5)3}] 3M,R which feature the rare ability to activate both dinitrogen and dihydrogen at a single metal center, except in the case where M=Mo and R=Ph for which fast precipitation of insoluble [Mo(H)4(dppe)2] (dppe=1,2-bis(diphenylphosphino)ethane) occurs. The frustrated Lewis pair (FLP)-related reactivity of the B-N linkage in compounds 3W,R was explored and led to distal N functionalization without involvement of the hydride ligands. It is shown in one example that the resulting bis(hydride) diazenido compounds may also be obtained through a sequence involving first FLP-type N-functionalization followed by oxidative addition of H2. Those oily compounds were found to have limited stability in solution or in their isolated states. Finally, treatment of 3W,Et with the Lewis base N,N-dimethylaminopyridine (DMAP) affords the simple but unknown bis(hydride)-dinitrogen species [W(H)2(depe)2(N2)] 11Et (depe=1,2-bis(diethylphosphino)ethane) which direct, selective formation from trans-[W(N2)2(depe)2] is not possible.

Synthesis and Characterization of a Copper Dinitrogen Complex Supported by a Weakly Coordinating Anion.

We report the synthesis and full characterization of the copper dinitrogen complex [(η1-N2)Cu{Al(ORF)4}] 2 (RF=C(CF3)3) prepared by a cascade metathesis reaction of Ag[Al(ORF)4] with CuI-excess in iso-perfluorohexane (i-pfh) under N2 atmosphere. Title compound 2 features an extraordinarily high N2 stretching frequency at 2313/2314 cm-1 (IR/Raman) and was characterized by single-crystal and powder X-ray diffractometry. Quantum chemical charge displacement analysis based on natural orbitals of chemical valence (CD-NOCV) indicates that the copper-dinitrogen interaction is still governed by weak π-backdonation, but is significantly reduced compared to all literature-known transition metal dinitrogen complexes.

Increase of secondary metabolites in sweet basil (Ocimum basilicum L.) leaves by exposure to N2O5 with plasma technology.

Exposure to N2O5 generated by plasma technology activates immunity in Arabidopsis through tryptophan metabolites. However, little is known about the effects of N2O5 exposure on other plant species. Sweet basil synthesizes many valuable secondary metabolites in its leaves. Therefore, metabolomic analyses were performed at three different exposure levels [9.7 (Ex1), 19.4 (Ex2) and 29.1 (Ex3) µmol] to assess the effects of N2O5 on basil leaves. As a result, cinnamaldehyde and phenolic acids increased with increasing doses. Certain flavonoids, columbianetin, and caryophyllene oxide increased with lower Ex1 exposure, cineole and methyl eugenol increased with moderate Ex2 exposure and L-glutathione GSH also increased with higher Ex3 exposure. Furthermore, gene expression analysis by quantitative RT-PCR showed that certain genes involved in the syntheses of secondary metabolites and jasmonic acid were significantly up-regulated early after N2O5 exposure. These results suggest that N2O5 exposure increases several valuable secondary metabolites in sweet basil leaves via plant defense responses in a controllable system.

Nitrogen Fixation by Manganese Complexes - Waiting for the Rush?

Manganese is currently experiencing a great deal of attention in homogeneous catalysis as a sustainable alternative to platinum group metals due to its abundance, affordable price and low toxicity. While homogeneous nitrogen fixation employing well-defined transition metal complexes has been an important part of coordination chemistry, manganese derivatives have been only sporadically used in this research area. In this contribution, the authors systematically cover manganese organometallic chemistry related to N2 activation spanning almost 60 years, identify apparent pitfalls and outline encouraging perspectives for its future development.

Catalytic Nitrogen Fixation Using Well-Defined Molecular Catalysts under Ambient or Mild Reaction Conditions.

Ammonia (NH3) is industrially produced from dinitrogen (N2) and dihydrogen (H2) by the Haber-Bosch process, although H2 is prepared from fossil fuels, and the reaction requires harsh conditions. On the other hand, microorganisms have fixed nitrogen under ambient reaction conditions. Recently, well-defined molecular transition metal complexes have been found to work as catalyst to convert N2 into NH3 by reactions with chemical reductants and proton sources under ambient reaction conditions. Among them, involvement of both N2-splitting pathway and proton-coupled electron transfer is found to be very effective for high catalytic activity. Furthermore, direct electrocatalytic and photocatalytic conversions of N2 into NH3 have been recently achieved. In addition to catalytic formation of NH3, selective catalytic conversion of N2 into hydrazine (NH2NH2) and catalytic silylation of N2 into silylamines have been reported. Catalytic C-N bond formation has been more recently established to afford cyanate anion (NCO-) under ambient reaction conditions. Further development of direct conversion of N2 into nitrogen-containing compounds as well as green ammonia synthesis leading to the use of ammonia as an energy carrier is expected.

Reductions of Arenes using a Magnesium-Dinitrogen Complex.

In this contribution, we present "Birch-type", and other reductions of simple arenes by the potassium salt of an anionic magnesium dinitrogen complex, [{K(TCHPNON)Mg}2(µ-N2)] (TCHPNON=4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene), which acts as a masked dimagnesium(I) diradical in these reactions. This reagent is non-hazardous, easy-to-handle, and in some cases provides access to 1,4-cyclohexadiene reduction products under relatively mild reaction conditions. This system works effectively to reduce benzene, naphthalene and anthracene through magnesium-bound "Birch-type" reduction intermediates. Cyclohexadiene products can be subsequently released from the magnesium centres by protonolysis with methanol. In contrast, the reduction of substituted arenes is less selective and involves competing reaction pathways. For toluene and 1,3,5-triphenylbenzene, the structural authentication of "Birch-type" reduction intermediates is conclusive, although the formation of corresponding 1,4-cyclohexadiene derivatives was low yielding. Reduction of anisole did not yield an isolable "Birch-type" intermediate, but instead gave a C-O activation product. Treating triphenylphosphine with [{K(TCHPNON)Mg}2(µ-N2)] resulted in the extrusion of both biphenyl and dinitrogen to afford a magnesium(II) phosphanide [{K(TCHPNON)Mg(µ-PPh2)}2]. Reduction of fluorobenzene proceeded via C-F activation of the arene, and isolation of the magnesium(II) fluoride [{K(TCHPNON)Mg(µ-F)}2]. Finally, the two-electron reduction of 1,3,5,7-cyclooctatetraene (COT) with [{K(TCHPNON)Mg}2(µ-N2)] yielded a complex, [{K(TCHPNON)Mg}2(µ-COT)], incorporating the aromatic dianion (COT2-).

[A case of acute inhalation dinitrogen tetroxide poisoning].

Dinitrogen tetroxide is often used as an oxidant in rocket propellant and has strong irritant and corrosive properties. This paper analyzes the clinical data of a patient with dinitrogen tetroxide poisoning admitted in the 63710 Army Hospital of Chinese People's Liberation Army, so as to further explore the poisoning mechanism, clinical characteristics and key points of acute inhaled dinitrogen tetroxide poisoning.

Unusual Electronic Structures of an Electron Transfer Series of [Cr(µ-η1 : η1 -N2 )Cr]0/1+/2.

In dinitrogen (N2 ) fixation chemistry, bimetallic end-on bridging N2 complexes M(µ-η1 : η1 -N2 )M can split N2 into terminal nitrides and hence attract great attention. To date, only 4d and 5d transition complexes, but none of 3d counterparts, could realize such a transformation. Likewise, complexes {[Cp*Cr(dmpe)]2 (µ-N2 )}0/1+/2+ (1-3) are incapable to cleave N2 , in contrast to their Mo congeners. Remarkably, cross this series the N-N bond length of the N2 ligand and the N-N stretching frequency exhibit unprecedented nonmonotonic variations, and complexes 1 and 2 in both solid and solution states display rare thermally activated ligand-mediated two-center spin transitions, distinct from discrete dinuclear spin crossovers. In-depth analyses using wave function based ab initio calculations reveal that the Cr-N2 -Cr bonding in complexes 1-3 is distinguished by strong multireference character and cannot be described by solely one electron configuration or Lewis structure, and that all intriguing spectroscopic observations originate in their sophisticate multireference electronic structures. More critical is that such multireference bonding of complexes 1-3 is at least a key factor that contributes to their kinetic inertness toward N2 splitting. The mechanistic understanding is then used to rationalize the disparate reactivity of related 3d M(µ-η1 : η1 -N2 )M complexes compared to their 4d and 5d analogs.

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach.

Dinitrogen trioxide (N2O3) is a potent nitrosating agent featured with high reactivity and appealing atom economy. Because of its instability and the entanglement of chemical and phase equilibria, N2O3 has rarely been utilized in organic synthesis as a stock reagent with well-defined composition. In this review, the preparations of pure N2O3 and its concentrated solution (>0.1 M) are discussed from the aspect of phase equilibrium. Understanding the physical and chemical characteristics of N2O3, along with how reaction parameters (temperature, pressure, molar ratio) interact, plays a crucial role in managing the concentration of N2O3 in the liquid phase. This control holds practical significance in achieving quantitative reactions.

Dominant physical and chemical processes impacting nitrate in Shandong of the North China Plain during winter haze events.

Nitrate has been a dominant component of PM2.5 since the stringent emission control measures implemented in China in 2013. Clarifying key physical and chemical processes influencing nitrate concentrations is crucial for eradicating heavy air pollution in China. In this study, we explored dominant processes impacting nitrate concentrations in Shandong of the North China Plain during three haze events from 9 to 25 December 2021, named cases P1 (94.46 (30.85) µg m-3 for PM2.5 (nitrate)), P2 (148.95 (50.12) µg m-3) and P3 (88.03 (29.21) µg m-3), by using the Weather Research and Forecasting/Chemistry model with an integrated process rate analysis scheme and updated heterogeneous hydrolysis of dinitrogen pentoxide on the wet aerosol surface (HET-N2O5) and additional nitrous acid (HONO) sources (AS-HONO). The results showed that nitrate increases in the three cases were attributed to aerosol chemistry, whereas nitrate decreases were due mainly to the vertical mixing process in cases P1 and P2 and to the advection process in case P3. HET-N2O5 (the reaction of OH + NO2) contributed 45 % (51 %) of the HNO3 production rate during the study period. AS-HONO produced a nitrate enhancement of 24 % in case P1, 12 % in case P2 and 19 % in case P3, and a HNO3 production rate enhancement of 0.79- 0.97 (0.18- 0.60) µg m-3 h-1 through the reaction of OH + NO2 (HET-N2O5) in the three cases. This study implies that using suitable parameterization schemes for heterogeneous reactions on aerosol and ground surfaces and nitrate photolysis is vital in simulations of HONO and nitrate, and the MOSAIC module for aerosol water simulations needs to be improved.

Rotational Transitions in the N2 + Ion Induced by Collisions with Helium Atoms in Cold Helium Plasmas. A Quasiclassical Trajectory Study.

Cross-sections of state-to-state rotational transitions in electronically ground-state 14 N 2 + ${{\rm{N}}_2^ + }$ (X2 Σ g + ${{\Sigma }_{g}^{+}}$ ) ions induced by collisions with 4 He atoms have been calculated using a quasiclassical trajectory method and a set of artificial neural networks representing the N 2 + ${{\rm{N}}_2^ + }$ /He potential energy surface. The training points for the neural networks have been calculated at a MCSCF (multi-configuration self-consistent field)/aug-cc-pVQZ level. A broad range of the N 2 + ${{\rm{N}}_2^ + }$ /He collision energy has been considered ( E c o l l ≤ 100 ${{E}_{{\rm c}{\rm o}{\rm l}{\rm l}}\le 100}$  eV) and the efficiency of vibrational transitions in the N 2 + ${{\rm{N}}_2^ + }$ ion has also been analyzed. It has been found that vibrational transitions are negligible with respect to rotational transitions up to E c o l l ≈ 10 ${{E}_{{\rm c}{\rm o}{\rm l}{\rm l}}\approx 10}$  eV and that above this energy, both rotational and vibrational transitions in N 2 + ${{\rm{N}}_2^ + }$ are marginal in the N 2 + ${{\rm{N}}_2^ + }$ /He collisions.

Screening seven-electron boron-centered radicals for dinitrogen activation.

The activation of dinitrogen is significant as nitrogen-containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO-LUMO gap (10.8 eV) and high bond dissociation energy (945 kJ mol-1 ) renders its activation under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate that a series of seven-electron (7e) boron-centered radical can be used to activate N2 via density functional theory calculations. It is found that boron-centered radicals containing amine ligand perform best on the thermodynamics of dinitrogen activation. In addition, when electron-donating groups are introduced at the boron atom, these radicals can be used to activate N2 with low reaction barriers. Further analysis suggests that the electron transfer from the boron atom to the π* orbitals of dinitrogen is essential for its activation. Our findings suggest great potential of 7e boron radicals in the field of dinitrogen activation.

Mineral and Carbon Metabolic Adjustments in Nodules of Symbiotically Grown Faba Bean (Vicia faba L.) Varieties in Response to Organic Phosphorus Supplementation.

Phosphorus (P) is a major limiting factor for legume and symbiotic nitrogen fixation (SNF). Although overall adaptations of legumes to P supplementation have been extensively studied in connection with inorganic P, little information is currently available regarding nodulation or SNF responses to organic P (Po) in hydroponics. We investigated the mineral and carbon metabolism of Po-induced nodules of two contrasting faba bean varieties grown hydroponically under inorganic P (Pi), viz., in P-deficient (2 µM KH2PO4, -Pi), sufficient-P (200 µM KH2PO4, +Pi), and phytic acid (200 µM, Po) conditions, and were inoculated with Rhizobium leguminosarum bv. viciae 3841 and grown for 30 days. The results consistently reveal similar growth and biomass partitioning patterns between +Pi and Po, with both varying substantially from -Pi. In comparison, +Pi and Po observed equivalent accumulations of overall elemental P concentrations, with both increasing by 114 and 119%, respectively, relative to -Pi. A principal component analysis on metabolites showed a clear separation of the -Pi treatment from the others, with +Pi and Po correlating closely together, highlighting the nonsignificant differences between them. Additionally, the δ15N abundance of shoots, roots, and nodules was not significantly different between treatments and varieties and exhibited negative δ15N signatures for all tissues. Our study provides a novel perspective on mineral and carbon metabolism and their regulation of the growth, functioning, and reprogramming of nodules upon phytate supply.

Coordination and Activation of N2 at Low-Valent Magnesium using a Heterobimetallic Approach: Synthesis and Reactivity of a Masked Dimagnesium Diradical.

The activation of dinitrogen (N2 ) by transition metals is central to the highly energy intensive, heterogeneous Haber-Bosch process. Considerable progress has been made towards more sustainable homogeneous activations of N2 with d- and f-block metals, though little success has been had with main group metals. Here we report that the reduction of a bulky magnesium(II) amide [(TCHP NON)Mg] (TCHP NON=4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) with 5 % w/w K/KI yields the magnesium-N2 complex [{K(TCHP NON)Mg}2 (µ-N2 )]. DFT calculations and experimental data show that the dinitrogen unit in the complex has been reduced to the N2 2- dianion, via a transient anionic magnesium(I) radical. The compound readily reductively activates CO, H2 and C2 H4 , in reactions in which it acts as a masked dimagnesium(I) diradical.

Automated rapid triple-isotope (δ15N, δ18O, δ17O) analyses of nitrate by Ti(III) reduction and N2O laser spectrometry.

The nitrogen and oxygen (δ15N, δ18O, δ17O) stable isotopic compositions of nitrate (NO3-) are crucial tracers of nutrient N sources and dynamics in aquatic and atmospheric systems. Methods to reduce aqueous NO3- to N2O gas (microbial or Cd method) before 15N and 18O isotope analyses require multi-step conversion or toxic chemicals, and 17O in N2O cannot be disentangled by IRMS due to isobaric interferences. This technical note describes the automation of the stable-isotope analyses of nitrate by coupling the new Ti method with a headspace autosampler and an N2O triple-isotope laser analyzer based on off-axis integrated cavity output spectroscopy. The automation yielded accurate and precise results for routine determinations of δ15N, δ18O, and δ17O values for aqueous nitrate in environmental waters. Systematic corrections were required for cavity pressure, N2O concentration and water vapour content to obtain the highest precision for all three isotopic ratios. For the first time, an automated laser-based system facilitates routine low-cost triple isotope analyses in studies where high-temporal resolution isotope analyses of NO3- are required but have been, until now, cost-prohibitive and time-consuming (e.g. atmospheric N pollution).