Stability of polynitrogen compounds: the importance of separating the sigma and pi electron systems.

  title={Stability of polynitrogen compounds: the importance of separating the sigma and pi electron systems.},
  author={Moran Noyman and Shmuel Zilberg and Yehuda Haas},
  journal={The journal of physical chemistry. A},
  volume={113 26},
Planar N(x) systems such as cyclo-N(5)(-) and N(5)(+) tend to be more stable than nonplanar systems such as the neutral cyclo-N(6). It is proposed that the key to stabilization is the separation of the sigma and pi electron systems. In both cyclo-N(5)(-) and N(5)(+), a six-pi-electron system is created upon either adding to or removing from the cyclo-N(5) radical one electron. Judicious addition of oxygen atoms to polynitrogen ring compounds such as cyclo-N(4) and cyclo-N(6) can increase their… 
What are the roles of N3 and N5 rings in designing polynitrogen molecules?
A series of polynitrogen molecules composed by multiple cyclic-N(3) and/or cyclic-N(5) are systematically investigated by using DFT and MP2 methods. It is found that all energetically favored
Recent advances in the syntheses and properties of polynitrogen pentazolate anion cyclo-N5- and its derivatives.
A detailed introduction to cyclo-N5- is provided and recent studies are summarized to improve the understanding of polynitrogen chemistry while supporting further research into its potential application as an efficient, safe, and environmentally friendly HEDM.
Computational insights into novel dicobalt polynitrogen: structure, stability, intermolecular interaction, and application
Previous studies have suggested that polynitrogen species are significant as potential candidates for superior energetic material. In this paper, the polynitrogen species of Co2(N5)4 were reasonably
Computational analysis of polyazoles and their N-oxides
The polyazoles have five-membered heterocyclic rings with N/C ratios of at least 2/3. Their high nitrogen contents result in relatively high crystal densities and large positive heats of formation,
Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study.
The present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations, and proposes 19 N-OXides as basic structures for high-energy materials with considerable stability.
The stability and decomposition mechanism of the catenated nitrogen compounds
The decomposition mechanism of the N,N’-azo azole poly-nitrogen compounds were obtained and the compounds with the decomposition caused by the rupture of the -N-N=N- N- bridge are more stable than the ones with the ring-opening decomposition mechanisms.
Structure, stability and intramolecular interaction of M(N5)2 (M = Mg, Ca, Sr and Ba) : a theoretical study
The potential energetic materials, alkaline earth metal complexes of the pentazole anion (M(N5)2, M = Mg2+, Ca2+, Sr2+ and Ba2+), were studied using the density functional theory. The stable
Stability of neutral molecular polynitrogens: energy content and decomposition mechanisms
The potential application of all-nitrogen molecules as high energy density materials (HEDMs) has been attracting considerable scientific effort. If stable enough to be synthesized and stored, these
From planes to cluster: The design of polynitrogen molecules
Polynitrogen compounds are a class of promising green high-energy-density materials. Using three-membered to six-memberd nitrogen rings, called all-nitrogen building blocks, a series of two


Besides N(2), What Is the Most Stable Molecule Composed Only of Nitrogen Atoms?
The increment scheme also provides estimates of the strain energies of polynitrogen compounds, e.g., tetraazatetrahedrane, octaazacubane, and N(20) (27, 294.6 kcal/mol), and is useful in searching for new high-energy-high-density materials.
Possible Products of the End-On Addition of N3- to N5+ and Their Stability
The recent synthesis of N5+[AsF6]- suggests the addition of N5+ and N3- as a possible route to N8. Because homoleptic polynitrogen compounds with more than three nitrogen atoms are nearly unknown and
Azabenzenes (azines) The nitrogen derivatives of benzene with one to six N atoms: Stability, homodesmotic stabilization energy, electron distribution, and magnetic ring current; a computational study
The twelve azabenzenes — the species formed by replacing CH groups of benzene by N — were examined computationally (with emphasis on the six contiguous-nitrogen species). MP2(fc)/6-31G*,
Recent Advances in the Chemistry of N5+, N5− and High-Oxygen Compounds
An overview of our work in the areas of polynitrogen and high-nitrogen and high-oxygen chemistry is given. Areas of interest include the synthesis and characterization of novel polynitrogen ions,
Structure and Stability of N6 Isomers and Their Spectroscopic Characteristics
Among homonuclear nitrogen molecules, N6 isomers occupy a critical position as a possible diazide or a benzene analogue. However, the character of stationary points on the N6 potential-energy
Stabilization of the Pseudo-Benzene N6 Ring with Oxygen
The long sought N6 ring that is isoelectronic with benzene can be formed by adding coordinate-covalent bonds from oxygen. Optimized structures, normal infrared harmonic frequencies, heats of
Confirmation of the "long-lived" tetra-nitrogen (N4) molecule using neutralization-reionization mass spectrometry and ab initio calculations.
Tetra-nitrogen (N(4)), which has been the subject of recent controversy, has been prepared from the N(4) (+) cation and then detected as a reionized gaseous metastable molecule with a lifetime exceeding 0.8 micros in experiments based on neutralization-reionization mass spectrometry.
Ab initio correlated calculations of six nitrogen (N6) isomers
MP2/6-31G*//MP2/6-31G* structures, energies, and vibrational frequencies have been calculated for six N[sub 6]/isomers. These isomers are the nitrogen analogues of the following carbon structures: