Stability of polynitrogen compounds: The importance of separating the σ and π electron systems

Moran Noyman, Shmuel Zilberg, Yehuda Haas

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59 Scopus citations

Abstract

Planar Nx systems such as cyclo-N5- and N5+ tend to be more stable than nonplanar systems such as the neutral cyclo-N6. It is proposed that the key to stabilization is the separation of the σ and π electron systems. In both cyclo-N 5- and N5+, a six-π-electron system is created upon either adding to or removing from the cyclo-N5 radical one electron. Judicious addition of oxygen atoms to polynitrogen ring compounds such as cyclo-N4 and cyclo-N6 can increase their thermodynamic and kinetic stabilities, accompanied by only a small reduction in their efficiency as high energy density materials (HEDMs). The properties of some of these compounds are calculated and compared with the parent all-nitrogen compounds. Coordination of one or more oxygen atoms to the ring leads to effective separation of the σ and π electron systems helping to stabilize the systems. Natural bond analysis indicates that the exocyclic NO bonds can assume a single or double bond character, depending on the ring system.

Original languageEnglish
Pages (from-to)7376-7382
Number of pages7
JournalJournal of Physical Chemistry A
Volume113
Issue number26
DOIs
StatePublished - 2 Jul 2009
Externally publishedYes

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