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Unifying Electric Field Catalysis with the Inductive Effect, Electro-Inductive Effect, and Differential
Vivekananda Samantaray1, Rajeev Ramanan1
1Department of Chemistry, National Institute of Technology, Rourkela, Odisha 769008, India.
The Journal of Organic Chemistry
|August 25, 2025
Summary
A new Electric Field Equivalent (EFEq) unifies catalysis from electric fields, substituents, and solvents. This value quantifies how molecular electron density changes impact reaction rates, offering a foundational concept for catalysis research.
Area of Science:
- Chemistry
- Physical Chemistry
- Catalysis
Background:
- Electric field (EF) catalysis, substituent effects, and differential solvation influence molecular electron density and reaction pathways.
- These effects modulate electron flow, leading to catalysis or inhibition in chemical reactions.
Purpose of the Study:
- To introduce a unified Electric Field Equivalent (EFEq) value.
- To quantify the impact of substituents and solvents on catalytic reactions.
- To establish a foundational concept connecting electronic effects to EF catalysis.
Main Methods:
- Utilized the oxidative addition of aryl bromides to Pd in Suzuki-Miyaura coupling as a model reaction.
- Defined EFEq based on the electric field needed to reach a reference reaction point.
- Correlated EFEq values with established parameters like Hammett constants and electro-inductive effects.
Main Results:
- Developed a unified EFEq value applicable to both substituents and solvents.
- Demonstrated that EFEq correlates with Hammett constants and electro-inductive effects for substituents.
- Showed that solvent EFEq values correlate with catalysis arising from differential solvation.
Conclusions:
- The EFEq concept provides a quantitative measure for electronic effects in catalysis.
- EFEq serves as an additive building block connecting substituent and solvation effects to EF catalysis.
- This unified approach offers a new perspective on understanding and manipulating catalytic processes.
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