Structure-Activity Relationships for 1,3-Dipolar Cycloaddition Reactions of Criegee Intermediates with Carbonyls
Zachary A Cornwell1, Jonas J Enders1, Bridget Ferris2
1Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States.
ACS Earth & Space Chemistry
|March 25, 2026
Summary
This study develops predictive models for atmospheric Criegee intermediates (CIs) reactivity with carbonyls. Structure-activity relationships using Hammett analysis and quantum calculations offer insights into unknown reaction rates.
Area of Science:
- Atmospheric Chemistry
- Chemical Kinetics
- Environmental Science
Background:
- Criegee intermediates (CIs) are crucial atmospheric oxidants formed from alkene ozonolysis.
- Direct kinetic data for many CI reactions with carbonyl compounds are lacking.
- Carbonyls are significant primary and secondary atmospheric pollutants.
Purpose of the Study:
- To develop structure-activity relationships (SARs) for predicting CI reaction rate constants.
- To investigate the reactivity of formaldehyde oxide (CH2OO) with various carbonyls.
- To improve the representation of CI chemistry in atmospheric models.
Main Methods:
- Application of Hammett analysis, frontier molecular orbital (FMO) theory, and global electrophilicity indices.
- Development of substituent-based predictive models using kinetic data.
- Utilizing low-cost quantum chemical calculations for parameter estimation.
Main Results:
- Established SARs that successfully predict rate constants for various CI-carbonyl reactions.
- Hammett constants provided the best correlations, while orbital energies offered a practical alternative.
- Explored the impact of substitution on CI reactivity and cycloaddition kinetics.
Conclusions:
- Predictive models enhance the understanding and representation of CI atmospheric chemistry.
- SARs are valuable tools for estimating unknown reaction rate constants.
- Quantum chemical methods offer a feasible approach for systems lacking experimental data.
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