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Updated: Jun 4, 2026
06:53
Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
HCB11(CF3)(n)F(11-n)-: inert anions with high anodic oxidation potentials
Matthew G Fete1, Zdeněk Havlas, Josef Michl
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, United States.
Journal of the American Chemical Society
|February 24, 2011
Summary
Cesium salts of carborane anions were synthesized and studied. Some salts are explosive, while others are stable, and their fluorinated derivatives show unique radical properties.
Area of Science:
- * Inorganic Chemistry
- * Organometallic Chemistry
- * Materials Science
Background:
- * Carborane anions are versatile building blocks in chemistry.
- * Fluorination of carboranes can significantly alter their properties.
- * Understanding the stability and reactivity of these anions is crucial for their applications.
Purpose of the Study:
- * To synthesize and characterize cesium salts of novel fluorinated carborane anions.
- * To investigate the stability and explosive properties of these new compounds.
- * To explore the redox behavior and radical formation of these carboranes.
Main Methods:
- * Synthesis of cesium salts via fluorination of methylated and iodinated carborane precursors.
- * Determination of gas-phase electron detachment energies using BL3YP/6-31G* calculations.
- * Oxidation studies using NiF3+ in anhydrous liquid HF at low temperatures.
- * Characterization of radical species using Electron Paramagnetic Resonance (EPR) spectroscopy.
Main Results:
- * Successful preparation of four cesium salts of fluorinated carborane anions.
- * Identification of explosive properties in neat Cs(+)[1-H-CB(11)(CF3)11]- and Cs(+)[CB(11)(CF3)12]-.
- * High gas-phase electron detachment energies (5-8 eV) for the studied anions.
- * Generation of stable, colored, EPR-active neutral radicals from anions with n=6 or 5 upon oxidation.
- * Quantitative recovery of original anions upon warming, indicating radical oxidation of the solvent.
Conclusions:
- * The fluorination degree and substitution pattern influence the stability and reactivity of carborane anions.
- * The synthesized carborane anions exhibit high electron detachment energies, suggesting strong electron-withdrawing effects.
- * Novel neutral carborane radicals can be generated and are stable at low temperatures.
- * The observed radical stability and subsequent decomposition pathway offer insights into carborane chemistry and potential applications.
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