In‐Plane Bishomoaromaticity in Tetranitrogen Dianions: Solid‐State, Solution, and Electronic Structures

Geier, Jens; Exner, Kai S.; Prinzbach, Horst

doi:10.1002/anie.200462126

Cited by 7 publications

(7 citation statements)

References 33 publications

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“…Although rare, similar trans-annular O,S‚‚‚Sb interactions have been topologically characterized based on theoretical calculations in dibenzostibocines; 47 S‚‚‚N in 1,5-triazocine; 49 S‚‚‚S in S 8 2+ ; 50,51 Se‚‚‚Se in Se 8 2+ 50 and N‚‚‚N in tetranitrogen dianions. 52 The C‚‚‚C interactions in [2.2]paracyclophane 53 and Si‚‚‚N in 1-methylsilatrane 54 have been analyzed based on both experimental and theoretical data. The N‚‚‚N critical point properties reported here are slightly smaller than in ref 52, which correlates with the longer N-N distance.…”

Section: Resultsmentioning

confidence: 99%

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

2007

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Chemical bonding in the beta-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N...N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O...O and O...C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.

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Section: Resultsmentioning

confidence: 99%

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

2007

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“…For example, despite formal 6p electrons in the π-system of N 4 2– , the corresponding NICS(1) is close to zero. Conversely, σ-aromaticity is higher, which was also found in the case of in-plane bishomoaromaticity of specifically preoriented bisdiazenes forming cyclic tetranitrogen dianions . It is also interesting to estimate ring strain energies (RSE) of the N 4 x – rings.…”

Section: Results and Discussionmentioning

confidence: 83%

“…Conversely, σ-aromaticity is higher, which was also found in the case of in-plane bishomoaromaticity of specifically preoriented bisdiazenes forming cyclic tetranitrogen dianions. 59 It is also interesting to estimate ring strain energies (RSE) of the N 4…”

Section: Resultsmentioning

confidence: 99%

Recoverability of N₄^x–Anions to Ambient Pressure: A First-Principles Study ofcyclo- andsyn-Tetranitrogen Units

Bondarchuk

2021

J. Phys. Chem. C

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In this paper, we have analyzed the possibility of various neutral and anionic forms of both cyclic and acyclic N4 species to be recovered to ambient conditions using state-of-the-art computational techniques. Phonon dispersion and mechanical properties calculations as well as ab initio molecular dynamics simulations revealed that syn-tetranitrogen units are kinetically stable only in the form of N4 4– anion. Meanwhile, salts of cyclic N4 (c-N4, tetrazete) with alkali, alkaline earth metals, and aluminum appeared to be dramatically stable at ambient conditions for a wide range of oxidation states of c-N4 x– from x = 1–3. Varying both metal and stoichiometry, one can obtain salts with a wide range of properties: band gap (1–5 eV), bulk modulus (36–196 GPa), enthalpy of formation (from −21 to 660 kJ mol–1), and so forth. Thus, crystal structure prediction and comprehensive characterization, which included bonding nature, stability criteria, spectral properties along with thermodynamic and energetic characteristics of c-N4 and its salts (Na2N8, Li2N4, MgN4, and AlN4) as well as calcium salt of syn-N4 4– (Ca2N4) are performed in this work. The obtained results significantly expand our understanding of the possible forms of nitrogen existence in nature, which, if synthesized, can find a number of interesting applications.

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“…The synthesis of some compounds with planar cyclic

{normalN}_{4}^{2 -}

ions are reported earlier . Geier et al in a combine experimental and theoretical study revealed the in‐plane bis‐homoaromaticity in tetranitrogen dianions. Exner et al showed that two electron reduction of comparably proximate bis‐diazenes presents the doorway to the nonclassical cyclic delocalized

{normalN}_{4}^{2 -}

dianion.…”

Section: Introductionmentioning

confidence: 84%

Guest–host interaction in an aza crown analog

Das

Chattaraj

2014

Int J of Quantum Chemistry

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Host–guest interactions in a new aza crown analog [normalN4normalC2normalH2]42− with alkali and alkaline earth metal ions are studied at different levels of theory. All the compounds are optimized at B3LYP/6‐311+G(d) level of theory. To build the general idea about the consequence of methods of computation on the interaction energy of metal ions with the ligand, geometry optimization of some selected planar systems are carried out at the M05‐2X, PBE0, wB97XD, and B3LYP‐D levels. Calculated geometrical parameters, interaction energies, nucleus‐independent chemical shift values, and thermodynamic properties highlight the selectivity associated with these interactions. Further insights into the nature of the bonding in these ion‐macrocyclic supramolecular units are obtained through the natural bond orbital, atoms‐in‐molecules, bond energy decomposition, and electron localization function analyses. © 2014 Wiley Periodicals, Inc.

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In‐Plane Bishomoaromaticity in Tetranitrogen Dianions: Solid‐State, Solution, and Electronic Structures

Cited by 7 publications

References 33 publications

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

Recoverability of N₄^x–Anions to Ambient Pressure: A First-Principles Study ofcyclo- andsyn-Tetranitrogen Units

Guest–host interaction in an aza crown analog

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In‐Plane Bishomoaromaticity in Tetranitrogen Dianions: Solid‐State, Solution, and Electronic Structures

Cited by 7 publications

References 33 publications

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

Recoverability of N4x–Anions to Ambient Pressure: A First-Principles Study ofcyclo- andsyn-Tetranitrogen Units

Guest–host interaction in an aza crown analog

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Recoverability of N₄^x–Anions to Ambient Pressure: A First-Principles Study ofcyclo- andsyn-Tetranitrogen Units