On the Formation of N3H3 Isomers in Irradiated Ammonia Bearing Ices: Triazene (H2NNNH) or Triimide (HNHNNH)

The remarkable versatility of triazenes in synthesis, polymer chemistry and pharmacology has led to numerous experimental and theoretical studies. Surprisingly, only very little is known about the most fundamental triazene: the parent molecule with the chemical formula N₃H₃. Here we observe molecular, isolated N₃H₃ in the gas phase after it sublimes from energetically processed ammonia and nitrogen films. Combining theoretical studies with our novel detection scheme of photoionization‐driven reflectron time‐of‐flight mass spectroscopy we can obtain information on the isomers of triazene formed in the films. Using isotopically labeled starting material, we can additionally gain insight in the formation pathways of the isomers of N₃H₃ under investigation and identify the isomers formed as triazene (H₂NNNH) and possibly triimide (HNHNNH).     

Insensitive Nitrogen‐Rich Materials Incorporating the Nitroguanidyl Functionality

A new class of nitroguanidyl‐functionalized nitrogen‐rich materials derived from 1,3,5‐triazine and 1,2,4,5‐tetrazine was synthesized through reactions between N‐nitroso‐N′‐alkylguanidines and the hydrazine derivatives of 1,3,5‐triazine or 1,2,4,5‐tetrazine. These compounds were fully characterized using multinuclear NMR and IR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). The heats of formation for all compounds were calculated with Gaussian 03 and then combined with experimental densities to determine the detonation pressures (P) and velocities (D_v) of the energetic materials. Interestingly, some of the compounds exhibit an energetic performance (P and D_v) comparable to that of RDX, thus holding promise for application as energetic materials.     

Catalytic effect of iron wires on the syntheses of ammonia and hydrazine in a radio-frequency discharge

The catalytic effect of iron wires on plasma syntheses of ammonia and hydrazine has been studied in the nitrogen-hydrogen plasma prepared using rf discharge at a pressure of 650 Pa (5 Torr). The product was mainly ammonia including a small amount of hydrazine. When iron wires were placed in the plasma downstream of the gas flow, the yields of both products increased, about two times in ammonia and two orders of magnitude in hydrazine. The yields increased with increasing number of wires (the surface area of the catalyst). The dissociative adsorption of nitrogen molecules and/or molecular ions on the iron surface and the formation of NH_x by the reaction with hydrogen in the plasma followed by the formation of NH₃ or N₂H₄ are considered as a reaction scheme. This is supported by the identification of NH₃ with XPS of the surface of iron wires.Partly presented at the 10th International Symposium on Plasma Chemistry, August 4–9, 1991, Bochum, Germany.     

活性氮与碘乙烷反应化学发光研究

在流动余辉装置上, 利用N₂空心阴极放电制备活性氮, 研究了活性氮与碘乙烷(C₂H₅I)反应的化学发光. 在620～820 nm波长范围内观察到了较强的发射光谱, 拟合得到的光谱常数表明它来源于NI(b¹Σ^＋→X³Σ^－)跃迁, 并对35个谱峰进行了振动归属. 最后讨论了活性氮中主要成分与C₂H₅I反应的可能过程, 结合辅助性实验分析表明, 活性氮中的N(²P)与C₂H₅I直接反应很可能产生激发态NI(b¹Σ^＋)自由基. 这是利用化学反应直接产生激发态NI(b¹Σ^＋)的首次报道, 观察到的激发态最高振动能级为v'＝6.     

NH3 Synthesis in the N2/H2 Reaction System using Cooperative Molecular Tungsten/Rhodium Catalysis in Ionic Hydrogenation: A DFT Study

The ionic hydrogenation of N₂ with H₂ to give NH₃ is investigated by means of density functional theory (DFT) computations using a cooperatively acting catalyst system. In this system, N₂ binds to a neutral tungsten pincer complex of the type [(PNP)W(N₂)₃] (PNP=pincer ligand) and is reduced to NH₃. The protons and hydride centers necessary for the reduction are delivered by heterolytic cleavage of H₂ between the N₂–tungsten complex and the cationic rhodium complex [Cp*Rh{2‐(2‐pyridyl)phenyl}(CH₃CN)]⁺. Successive transfer of protons and hydrides to the bound N₂, as well as all N_xH_y units that occur during the reaction, enable the computation of closed catalytic cycles in the gas and in the solvent phase. By optimizing the pincer ligands of the tungsten complex, energy spans as low as 39.3 kcal mol^?1 could be obtained, which is unprecedented in molecular catalysis for the N₂/H₂ reaction system.     

On the mechanism of the reduction of molecular nitrogen with aryldicyclopentadienyltitanium(III) complexes

The first step in the reduction of the dinitrogen ligand in (Cp₂TiR)₂N₂ (R  C₆H₅, m-, p-CH₃C₆H₄, C₆F₅, CH₂C₆H₅) by sodium napthalene (NaC₁₀H₈) involves the removal of one Cp group per titanium atom. The resulting diimide precursor reacts with a second mole of NaC₁₀H₈ with formation of a hydrazine precursor. This compound is thermally unstable and decomposes to an ammonia precursor. A minor part of the hydrazine precursor abstracts a proton from the solvent.     

Light Alters the NH3 vs N2H4 Product Profile in Iron-catalyzed Nitrogen Reduction via Dual Reactivity from an Iron Hydrazido (Fe=NNH2) Intermediate

Whereas synthetically catalyzed nitrogen reduction (N₂R) to produce ammonia is widely studied, catalysis to instead produce hydrazine (N₂H₄) has received less attention despite its considerable mechanistic interest. Herein, we disclose that irradiation of a tris(phosphine)borane (P₃^B) Fe catalyst, P₃^BFe⁺, significantly alters its product profile to increase N₂H₄ versus NH₃; P₃^BFe⁺ is otherwise known to be highly selective for NH₃. We posit a key terminal hydrazido intermediate, P₃^BFe=NNH₂, as selectivity-determining. Whereas its singlet ground state undergoes protonation to liberate NH₃, a low-lying triplet excited state leads to reactivity at N_α and formation of N₂H₄. Associated electrochemical and spectroscopic studies establish that N₂H₄ lies along a unique product pathway; NH₃ is not produced from N₂H₄. Our findings are distinct from the canonical mechanism for hydrazine formation, which proceeds via a diazene (HN=NH) intermediate and showcase light as a tool to tailor selectivity.     

Reactivity of digallane toward nitrogen-containing compounds

The reactions of [LGa–GaL] (L = dpp-bian = 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene) with ammonia and pyrrolidine in toluene lead to the formation of adducts [L(NH₃)Ga–Ga(NH₃)L], [L(HNC₄H₈)Ga–GaL] and [L(HNC₄H₈)Ga–Ga(HNC₄H₈)L], respectively. In contrast, the reaction between crystalline digallane and an excess of pyrrolidine leads to the formation of compound [LGa(NC₄H₈)(HNC₄H₈)]. The complex [LGa(C₅H₅N)(μ-O)Ga(C₅H₅N)L] was obtain from reaction of digallane with N₂O in the presence of pyridine.     

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Understanding the coordination of dinitrogen to iron is important for understanding biological nitrogen fixation as well as for designing synthetic systems that are capable of reducing N₂ to NH₃ under mild conditions. This review discusses recent advances in iron–dinitrogen coordination complexes and describes the factors that contribute to the degree of activation of the coordinated N₂. The reactivity of the N₂ ligand is also reviewed, with an emphasis on protonation reactions that yield ammonia and/or hydrazine. Coordination complexes containing N₂ reduction intermediates such as diazene (N₂H₂), hydrazido (N₂H₂^2?), hydrazine (N₂H₄), nitride (N^3?), imide (NH^2?), and amide (NH₂^?) are also discussed in the context of the mechanism of N₂ reduction to NH₃ mediated by iron coordination complexes.     

Mechanism of the reduction of molecular nitrogen to hydrazine by niobium (iii) hydroxide

The effect of the concentration of water on the rate of reduction of molecular nitrogen to hydrazine by niobium(iii) hydroxide in alkaline H₂O−MeOH and D₂O−MeOD mixtures was studied. In both cases, the reaction rate is maximum when [H₂O]=4 mol L⁻¹, and the inverse isotopic effect (K ^D/k ^H>1) is observed when [H₂O]<20 mol L⁻¹. Similar regularity was observed for the reaction of hydrogen elimination. It was found that HD is formed in the H₂O−MeOH system in the presence of D₂. The conclusion was made that the ratedetermining stage in hydrazine formation is the transfer of a hydride ion to the dinitrogen molecule coordinated to the binuclear Nb^III center. A kinetic scheme satisfactorily explaining the effect of the concentration of water ([H₂O]=1.5−49.0 mol L⁻¹) on the reaction rate constant was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1600–1604, September, 1997.     

Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage

Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H₂ release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η⁶‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc.     

Reactivity of TpMe2‐Supported Yttrium Alkyl Complexes toward Aromatic N‐Heterocycles: Ring‐Opening or CC Bond Formation Directed by CH Activation

Unusual chemical transformations such as three‐component combination and ring‐opening of N‐heterocycles or formation of a carbon–carbon double bond through multiple C–H activation were observed in the reactions of Tp^Me2‐supported yttrium alkyl complexes with aromatic N‐heterocycles. The scorpionate‐anchored yttrium dialkyl complex [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with 1‐methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24‐membered rare‐earth metallomacrocyclic compound [Tp^Me2Y(μ‐N,C‐Im)(η²‐N,C‐Im)]₆ ( 1 ; Im=1‐methylimidazolyl) through two kinds of C–H activations at the C2‐ and C5‐positions of the imidazole ring. However, [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with two equivalents of 1‐methylbenzimidazole to afford a C–C coupling/ring‐opening/C–C coupling product [Tp^Me2Y{η³‐(N,N,N)‐N(CH₃)C₆H₄NHCH?C(Ph)CN(CH₃)C₆H₄NH}] ( 2 ). Further investigations indicated that [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C–C coupling/ring‐opening product {(Tp^Me2)Y[μ‐η²:η¹‐SC₆H₄N(CH?CHPh)](THF)}₂ ( 3 ). Moreover, the mixed Tp^Me2/Cp yttrium monoalkyl complex [(Tp^Me2)CpYCH₂Ph(THF)] reacted with two equivalents of 1‐methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp^Me2CpY(μ‐N,C‐Im)]₃ ( 5 ), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp^Me2Y(Im‐Tp^Me2)] ( 7 ; Im‐Tp^Me2=1‐methyl‐imidazolyl‐Tp^Me2) and [Cp₃Y(HIm)] ( 8 ; HIm=1‐methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a C?C bond through multiple C–H activations.     

Towards Green Ammonia Synthesis through Plasma-Driven Nitrogen Oxidation and Catalytic Reduction

Ammonia is an industrial large-volume chemical, with its main application in fertilizer production. It also attracts increasing attention as a green-energy vector. Over the past century, ammonia production has been dominated by the Haber–Bosch process, in which a mixture of nitrogen and hydrogen gas is converted to ammonia at high temperatures and pressures. Haber–Bosch processes with natural gas as the source of hydrogen are responsible for a significant share of the global CO₂ emissions. Processes involving plasma are currently being investigated as an alternative for decentralized ammonia production powered by renewable energy sources. In this work, we present the PNOCRA process (plasma nitrogen oxidation and catalytic reduction to ammonia), combining plasma-assisted nitrogen oxidation and lean NO_x trap technology, adopted from diesel-engine exhaust gas aftertreatment technology. PNOCRA achieves an energy requirement of 4.6 MJ mol⁻¹ NH₃, which is more than four times less than the state-of-the-art plasma-enabled ammonia synthesis from N₂ and H₂ with reasonable yield (>1 %).     

Synthesis of novel 5H‐Pyrimido[5,4‐b]mdole‐(1H,3H)2,4‐diones as potential ligands for the cloned α1‐adrenoceptor subtypes

A new series of 3‐[ω‐[4‐(4‐substituted phenyl)piperazin‐1‐yl]alkyl]‐5H‐pyrimido[5,4‐b]indole‐(1H,3H)‐2,4‐diones ( 3–10 and 12–13 ) were synthesized from the N‐(2‐chloroethyl)‐N'‐[3‐(2‐ethoxycarbonyl)indolyl] urea ( 1 ) or the N‐(3‐chloropropyl)‐N'‐[3‐(2‐ethoxycarbonyl)indolyl] urea ( 2 ) and a number of 1‐(4‐substi‐tuted‐phenyl)piperazines. 3‐[2‐[4‐(4‐Aminophenyl)piperazin‐1‐yl]ethyl]‐5H‐pyrimido[5,4‐b]indole‐(1H,3H)2,4‐dione ( 14 ) was obtained by reduction of the parent nitro compound 8 . The obtained 5H‐pyrimido[5,4‐b]indole‐(1H,3H)2,4‐dione derivatives were tested towards cloned α_1A, α_1B and α_1D adrenergic receptors subtypes in binding assays. Some compounds showed good affinity and selectivity for the α_1D‐adrenoceptor subtype.     

Bioelectrochemical Haber–Bosch Process: An Ammonia‐Producing H2/N2 Fuel Cell

Nitrogenases are the only enzymes known to reduce molecular nitrogen (N₂) to ammonia (NH₃). By using methyl viologen (N ,N ′‐dimethyl‐4,4′‐bipyridinium) to shuttle electrons to nitrogenase, N₂ reduction to NH₃ can be mediated at an electrode surface. The coupling of this nitrogenase cathode with a bioanode that utilizes the enzyme hydrogenase to oxidize molecular hydrogen (H₂) results in an enzymatic fuel cell (EFC) that is able to produce NH₃ from H₂ and N₂ while simultaneously producing an electrical current. To demonstrate this, a charge of 60 mC was passed across H₂ /N₂ EFCs, which resulted in the formation of 286 nmol NH₃ mg⁻¹ MoFe protein, corresponding to a Faradaic efficiency of 26.4 %.     

Syntheses,Crystal Structures and Properties of a Series of 3D Metal–Inorganic Frameworks Containing Pentazolate Anion

Pentazolate anion (cyclo‐N₅^?), and/or N₃^?, NO₃^? were used as the ligands to obtain a series of nitrogen‐rich energetic three‐dimensional (3D) frameworks [Cu(N₅)(N₃)]_n, [Ag(N₅)]_n, [Ba(N₅)(NO₃)(H₂O)₃]_n, and [NaBa₃(N₅)₆(NO₃)(H₂O)₃]_n by self‐assembly. These frameworks were characterized by single‐crystal X‐ray diffraction, SEM, IR and Raman spectroscopy, elemental analysis, and thermal analysis. All the frameworks exhibited regular supramolecular structures and excellent stabilities at room temperature which can be attributed to the strong coordination bonds between cyclo‐N₅^? anions and metal ions. The successful stabilization of the cyclo‐N₅^? in more 3D multi‐ligand metal‐N₅^? frameworks after Na‐N₅^? frameworks has been demonstrated. This breakthrough offers new opportunities for the future of metal‐pentazolate frameworks and polynitrogen chemistry.     

A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity

Low‐valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square‐planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH₂CH₂P(tBu)₂)₂) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)]⁺. The Os^IV complex shows ambiphilic nitride reactivity with SiMe₃Br and PMe₃, respectively. Importantly, the hydrogenolysis with H₂ gives ammonia and the polyhydride complex [OsH₄(HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low‐valent osmium nitrides and of heterolytic H₂ activation for ammonia synthesis with H₂ under basic conditions.     

Hydrogenated Bismuth Molybdate Nanoframe for Efficient Sunlight‐Driven Nitrogen Fixation from Air

Sunlight‐driven dinitrogen fixation can lead to a novel concept for the production of ammonia under mild conditions. However, the efficient artificial photosynthesis of ammonia from ordinary air (instead of high pure N₂) has never been implemented. Here, we report for the first time the intrinsic catalytic activity of Bi₂MoO₆ catalyst for direct ammonia synthesis under light irradiation. The edge‐exposed coordinatively unsaturated Mo atoms in an Mo?O coordination polyhedron can act as activation centers to achieve the chemisorption, activation, and photoreduction of dinitrogen efficiently. Using that insight as a starting point, through rational structure and defect engineering, the optimized Bi₂MoO₆ sunlight‐driven nitrogen fixation system, which simultaneously possesses robust nitrogen activation ability, excellent light‐harvesting performance, and efficient charge transmission was successfully constructed. As a surprising achievement, this photocatalytic system demonstrated for the first time ultra‐efficient (1.3 mmol g^?1 h^?1) and stable sunlight‐driven nitrogen fixation from air in the absence of any organic scavengers.     

Cocrystals of 6‐methyl‐2‐thiouracil: presence of the acceptor–donor–acceptor/donor–acceptor–donor synthon

The results of seven cocrystallization experiments of the antithyroid drug 6‐methyl‐2‐thiouracil (MTU), C₅H₆N₂OS, with 2,4‐diaminopyrimidine, 2,4,6‐triaminopyrimidine and 6‐amino‐3H‐isocytosine (viz. 2,6‐diamino‐3H‐pyrimidin‐4‐one) are reported. MTU features an ADA (A = acceptor and D = donor) hydrogen‐bonding site, while the three coformers show complementary DAD hydrogen‐bonding sites and therefore should be capable of forming an ADA/DAD N—H...O/N—H...N/N—H...S synthon with MTU. The experiments yielded one cocrystal and six cocrystal solvates, namely 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–1‐methylpyrrolidin‐2‐one (1/1/2), C₅H₆N₂OS·C₄H₆N₄·2C₅H₉NO, (I), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine (1/1), C₅H₆N₂OS·C₄H₆N₄, (II), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylacetamide (2/1/2), 2C₅H₆N₂OS·C₄H₆N₄·2C₄H₉NO, (III), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylformamide (2/1/2), C₅H₆N₂OS·0.5C₄H₆N₄·C₃H₇NO, (IV), 2,4,6‐triaminopyrimidinium 6‐methyl‐2‐thiouracilate–6‐methyl‐2‐thiouracil–N,N‐dimethylformamide (1/1/2), C₄H₈N₅⁺·C₅H₅N₂OS⁻·C₅H₆N₂OS·2C₃H₇NO, (V), 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–N,N‐dimethylformamide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₃H₇NO, (VI), and 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–dimethyl sulfoxide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₂H₆OS, (VII). Whereas in cocrystal (I) an R₂²(8) interaction similar to the Watson–Crick adenine/uracil base pair is formed and a two‐dimensional hydrogen‐bonding network is observed, the cocrystals (II)–(VII) contain the triply hydrogen‐bonded ADA/DAD N—H...O/N—H...N/N—H...S synthon and show a one‐dimensional hydrogen‐bonding network. Although 2,4‐diaminopyrimidine possesses only one DAD hydrogen‐bonding site, it is, due to orientational disorder, triply connected to two MTU molecules in (III) and (IV).     

Two-path reduction of molecular nitrogen by transition metal hydroxides

The kinetics of the reduction of N₂ to N₂H₄ and NH₃ by Ti^III-Mo^III hydroxide was studied at pH I I and 303-333 K, and the activation energies for these reactions and also for the reaction N₂H₄ 2 NH₃ were determined (29, 70, and 25 kJ mol^– respectively). It was concluded that -90 % of ammonia was formed by the direct reduction of N₂ without intermediate formation of hydrazine. A mechanism of this reaction is suggested, which includes the proton insertion into the N-N bond favored by an enhanced electron density at the nitrogen atoms, according to the data of the quantum-mechanical calculation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1402–1405, June, 1996.