Structure cristalline de l'anhydride azotique, N<sub>2</sub>O<sub>5</sub>

Grison, E.; Eriks, K.; Vries, J. L. de

doi:10.1107/s0365110x50000744

Cited by 50 publications

(14 citation statements)

References 2 publications

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“…It is not clear, if such complexes actually exist in the gas phase. However, it is known that crystalline N 2 O 5 consists of nitronium and nitrate ions with six N···O contacts of 2.724 Å [28], but its sublimation occurs in form of N 2 O 5 molecules. Volatility of both neutral complexes, Fe(NO 3 ) 3 and Zr(NO 3 ) 4 , is well documented in [10] and [7], respectively.…”

Section: Resultsmentioning

confidence: 99%

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Tikhomirov¹,

Morozov²,

Znamenkov³

et al. 2002

Z. anorg. allg. Chem.

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Crystalline NO 2 [Fe(NO 3 ) 4 ] was obtained by dehydration of a solution of Fe(NO 3 ) 3 in 100 % HNO 3 and subsequent sublimation. NO 2 [Zr(NO 3 ) 5 ] was synthesized by reaction of ZrCl 4 with N 2 O 5 followed by sublimation in vacuum. X-ray single crystal structure determination showed both compounds to consist of nitronium cations, NO 2 ϩ , and nitratometalate anions. N-O distances in the linear NO 2 ϩ cations are in the range of 1.08Ϫ1.13 Å . In both [Fe(NO 3 ) 4 ] Ϫ and [Zr(NO 3 ) 5 ] Ϫ anions, all nitrate groups are coordinated bidentately with average M-O distances 2.134 and Neue Flüchtige Nitrylnitratometallate: NO 2 [Fe(NO 3 ) 4 ] und NO 2 [Zr(NO 3 ) 5 ] ؊ Synthese und Kristallstruktur Inhaltsübersicht. Kristallines NO 2 [Fe(NO 3 ) 4 ] wurde durch Einengen einer Lösung von Fe(NO 3 ) 3 in 100%iger HNO 3 und nachfolgender Sublimation des erhaltenen Feststoffes hergestellt. NO 2 [Zr(NO 3 ) 5 ] wurde durch Reaktion von ZrCl 4 mit N 2 O 5 und anschließender Vakuumsublimation synthetisiert. Die Röntgenein-kristallstrukturanalyse zeigt, dass beide Verbindungen aus Nitrylkationen, NO 2 ϩ , und Nitratometallatanionen bestehen. Die N-OAbstände in den linearen NO 2 ϩ -Kationen liegen im Bereich von 1.08Ϫ1.13 Å . In den [Fe(NO 3 ) 4 ] Ϫ -und [Zr(NO 3 ) 5 ] Ϫ -Anionen sind

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Section: Resultsmentioning

confidence: 99%

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Tikhomirov¹,

Morozov²,

Znamenkov³

et al. 2002

Z. anorg. allg. Chem.

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“…34 The nitronium ion is a well-known electrophile in nitration reactions. N 2 O 5 forms an ionic crystal with distinct nitronium and nitrate ions (NO 2 + and NO 3 À ).…”

Section: Introductionmentioning

confidence: 99%

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films

Hammerich

Finlayson-Pitts

Gerber

2015

Phys. Chem. Chem. Phys.

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Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.

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“…NO 2 + , which exhibits a symmetrical linear configuration (O=N + =O), is a main attacking reagent involved in nitrification because it can strongly withdraw electrons …”

Section: Resultsmentioning

confidence: 99%

“…NO 2 + ,w hich exhibits as ymmetricall inear configuration (O=N + =O), is am ain attacking reagenti nvolved in nitrification because it can strongly withdraw electrons. [36] Figure 1s hows the free-energy profiles of the nitration of glyoximew ith NO 2 + as the attacker in the ether solvent model obtained from B3LYP/6-311 ++G** (black solid) and CCSD(T)// B3LYP/6-311 ++G** (pink dashed) calculations.T he computed geometries of all energy minima and transition states are shown in Figure 2. The IRC paths being determined to ensure the accuracyo ft he transition states involved in the reaction and the atomicc oordinates of relevant stationary points are given in the Supporting Information (FigureS4a tions;asaresult, s complexes with nitryl groups and hydrogen ions (H + )a re generated.…”

Section: Computationalmethodsmentioning

confidence: 99%

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

et al. 2016

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The reaction pathway of the formation of 3,4-dinitrofuroxan from glyoxime is theoretically investigated under experimental conditions with 25 % nitric acid and dinitrogentetroxide reagents to clarify the mechanism of formation of a furoxan ring by glyoxime. The geometric configurations of minima and transition-state species are optimized at the (U)B3LYP/6-311++G** level. The CCSD(T) and CASSCF(10e,8o)/CASSCF(9e,8o) single-point energy corrections at the same level are performed on top of the optimized geometries. A subsequent dynamic correlation by using NEVPT2/6-311++G**-level single-point energy calculations based on the CASSCF results is also performed to obtain accurate energy values. The formation reaction is analyzed from two processes: glyoxime nitration and 3,4-dinitroglyoxime (nitration product) oxidative cyclization. Calculation results indicate that the electrophilic substitution of nitronium ions from the protonated HNO3 and the abstraction of hydrogen ions by HNO3 molecules are requisites of glyoxime nitration. The formation of a furoxan ring from 3,4-dinitroglyoxime involves two possible mechanisms: 1) oxydehydrogenation by NO2 molecules and the subsequent torsion of NO radical groups to form a ring and 2) the alternation of dehydrogenation and cyclization. The intermediates and transition states in both routes exhibit monoradical and diradical characteristics. Singlet and triplet reactions are considered for the diradical species. Results show that the singlet reaction mechanism is more favorable for cyclization than the triplet reaction. The formation of a furoxan ring from oxime is in accordance with the stepwise intermolecular dehydrogenation and intramolecular torsion to the ring.

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Structure cristalline de l'anhydride azotique, N₂O₅

Cited by 50 publications

References 2 publications

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

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Structure cristalline de l'anhydride azotique, N2O5

Cited by 50 publications

References 2 publications

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl−on aqueous films

Reaction Mechanism of 3,4‐Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime

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Structure cristalline de l'anhydride azotique, N₂O₅

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films