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Related Experiment Videos

The Dinitramide Anion, N(NO(2))(2)(-).

Karl O. Christe1, William W. Wilson, Mark A. Petrie

  • 1Hughes STX, Phillips Laboratory, Propulsion Directorate, Edwards Air Force Base, California 93524, Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, California 90089-1661, United Technologies Research Center, East Hartford, Connecticut 06108, SRI International, Menlo Park, California 94025, and Naval Research Laboratory, Washington, DC 20375-5341.

Inorganic Chemistry
|August 14, 1996
PubMed
Summary
This summary is machine-generated.

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The vibrational spectra of dinitroamide salts reveal that counterions and physical state significantly alter the N(NO2)2- anion structure. Calculations suggest C2 symmetry, but solution studies indicate C1 symmetry due to a low rotational barrier.

Area of Science:

  • Spectroscopy
  • Computational Chemistry
  • Solid-State Chemistry

Background:

  • The dinitroamide anion, N(NO2)2-, is an interesting subject due to its potential applications.
  • Understanding its structural and vibrational properties is crucial for predicting its behavior in various chemical environments.

Purpose of the Study:

  • To investigate the vibrational spectra of N(NO2)2- salts in solid and solution states.
  • To elucidate the influence of counterions (NH4+, K+, Cs+) and physical state on the anion's structure.
  • To compare experimental findings with theoretical ab initio calculations.

Main Methods:

  • Infrared (IR) and Raman spectroscopy were employed to measure vibrational spectra.
  • Ab initio calculations (HF/6-31G and MP2/6-31+G) were performed to assign spectral features.

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  • Raman polarization measurements were used to probe symmetry in solution.

    • Main Results:

    • Vibrational spectra of N(NO2)2- were strongly influenced by counterions and physical state, correlating with crystal structure variations.
    • Ab initio calculations predicted a minimum energy structure with C2 symmetry for the free N(NO2)2- ion.
    • Raman polarization data suggested a C1 (no symmetry) point group for the anion in solution.

    Conclusions:

    • The N(NO2)2- anion's structure is flexible and sensitive to its environment.
    • A very small N-NO2 rotational barrier (<3 kcal/mol) facilitates easy deformation, leading to a loss of symmetry in solution.
    • Experimental and computational results highlight the dynamic nature of the dinitroamide anion.