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Fluoro-nitrogen Cations.

Ashwani Vij1, William W Wilson1, Ralf Haiges1

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Angewandte Chemie (International Ed. in English)
|December 14, 2021
PubMed
Summary
This summary is machine-generated.

This study determined crystal structures of novel fluoro-nitrogen cations, revealing that N-F bond length shortens with increased fluorine and nitrogen s-character. Previous unusual bond lengths were due to structural disorder.

Keywords:
Fluoro-NitrogenFluoroammoniumFluorodiazoniumFluoronitroniumTrifluoro-Diazenium

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Area of Science:

  • Inorganic Chemistry
  • Solid-State Chemistry
  • Crystallography

Background:

  • Fluoro-nitrogen cations are important in various chemical applications.
  • Limited structural data exists for simple fluoro-nitrogen cations.
  • Understanding N-F bond characteristics is crucial for predicting chemical behavior.

Purpose of the Study:

  • To determine the crystal structures of novel fluoro-nitrogen cations: [NH3F]+, [NH2F2]+, and [N2F3]+.
  • To investigate the relationship between nitrogen hybridization, fluorine substitution, and N-F bond lengths.
  • To clarify discrepancies in previously reported N-F bond lengths.

Main Methods:

  • Single-crystal X-ray diffraction was used to determine the crystal structures.
  • Systematic analysis of N-F bond lengths across a series of related cations.
  • Comparison of experimental findings with theoretical predictions.

Main Results:

  • The crystal structures of [NH3F]+[CF3SO3]-, [NH2F2]+[SbF6]-, and [N2F3]+[Sb3F16]- were successfully characterized.
  • N-F bond length decreases from 1.40 Å to 1.26 Å with increasing fluorine substitution and nitrogen s-character.
  • Observed variations in N-F bond lengths are attributed to nitrogen atom hybridization and fluorine substitution levels.

Conclusions:

  • The study provides the first structural characterizations of these specific fluoro-nitrogen cations.
  • A clear trend of N-F bond shortening is established with increasing fluorination and nitrogen s-character.
  • Disorder in previous studies was identified as the cause of anomalous N-F bond length values.