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The high insolubility of some precipitates can result in an unfavorable relative supersaturation. This can lead to colloidal particles with a large surface-to-mass ratio, where adsorption is promoted. For instance, in the precipitation of silver chloride, silver ions are adsorbed on the surface of the colloidal particles, forming a primary layer. This layer attracts ions of opposite charge (such as nitrate ions), forming a diffuse secondary layer of adsorbed ions. This electric double layer...
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Do Corroles Stabilize Tetravalent Antimony?

Simon Eulberg1, Nina Schulze1, Jens Krumsieck1

  • 1Institute of Inorganic and Analytical Chemistry, TU Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.

Angewandte Chemie (International Ed. in English)
|June 15, 2023
PubMed
Summary
This summary is machine-generated.

Researchers synthesized novel antimony corrole cations, revealing structural insights and electronic properties. These compounds exhibit unique redox behavior, forming antimony(V) derivatives in the presence of water or fluoride.

Keywords:
AntimonyCorroleLigand RadicalsNon-InnocencePorphyrinoids

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Antimony corroles are macrocyclic compounds with unique electronic and structural properties.
  • Previous studies have focused on antimony(III) and antimony(V) complexes, with limited exploration of antimony corrole cations.

Purpose of the Study:

  • To synthesize and characterize novel antimony corrole cations through one-electron oxidation.
  • To investigate the structural, electronic, and redox properties of these new antimony corrole species.
  • To explore the reactivity of antimony corrole cations in the presence of water and fluoride.

Main Methods:

  • One-electron oxidation of antimony(III) corroles using silver(I) and copper(II) salts.
  • X-ray crystallography for structural determination.
  • Electron Paramagnetic Resonance (EPR) spectroscopy to study electronic properties.
  • Density Functional Theory (DFT) analysis for electronic structure calculations.

Main Results:

  • Successful isolation and crystallization of antimony corrole cations for the first time.
  • X-ray crystallography confirmed structural similarities with antimony(III) corroles.
  • EPR experiments revealed strong hyperfine interactions with 121Sb and 123Sb nuclei.
  • DFT analysis indicated the oxidized form is primarily a SbIII corrole radical with minimal SbIV character.
  • Redox disproportionation reactions were observed, yielding antimony(III) corroles and novel antimony(V) derivatives (difluorido- or oxido-antimony(V)corroles) via hydroxo-antimony(V) intermediates.

Conclusions:

  • The study reports the first successful synthesis and characterization of antimony corrole cations.
  • The findings provide crucial insights into the electronic structure and redox behavior of antimony corrole systems.
  • The observed redox disproportionation opens avenues for synthesizing new antimony(V) corrole complexes with potential applications.