Related Experiment Videos
The trifluoromethoxycarbonyl radical CF(3)OCO
Stefan von Ahsen1, Julia Hufen, Helge Willner
1Anorganische Chemie, Gerhard Mercator Universität Duisburg, Lotharstrasse1, 47048 Duisburg, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 14, 2002
Summary
The trifluoromethoxycarbonyl radical (CF(3)OCO) was synthesized and identified in a CO matrix. This radical is formed from specific precursors and dissociates under UV light, yielding trifluoromethyl radicals and carbon dioxide.
Area of Science:
- Chemical kinetics
- Spectroscopy
- Quantum chemistry
Background:
- The trifluoromethoxycarbonyl radical (CF(3)OCO) is a reactive intermediate.
- Understanding its formation and properties is crucial for radical chemistry.
Purpose of the Study:
- To synthesize and characterize the CF(3)OCO radical.
- To investigate its formation pathways and photochemical behavior.
Main Methods:
- Low-pressure flash pyrolysis of specific peroxy compounds.
- Matrix isolation spectroscopy (IR and UV).
- Density Functional Theory (DFT) calculations.
Main Results:
- The CF(3)OCO radical was successfully synthesized and trapped in a CO matrix.
- Experimental IR spectra matched DFT predictions, identifying the trans rotamer.
- The reaction of CF(3)O radicals with CO is exothermic by 33.6 kJ/mol.
- UV irradiation (λ<370 nm) caused CF(3)OCO to dissociate into CF(3) and CO(2).
Conclusions:
- The trans-CF(3)OCO radical was identified in a CO matrix.
- The radical is photochemically labile, dissociating into CF(3) and CO(2).
- CF(3) radicals do not react with solid CO to form CF(3)CO.