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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radical Formation: Addition00:47

Radical Formation: Addition

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Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

4.0K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.0K
Radical Formation: Overview01:03

Radical Formation: Overview

2.1K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

1.9K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
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Radical Polarity.

Jacob J A Garwood1, Andrew D Chen1, David A Nagib1

  • 1Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.

Journal of the American Chemical Society
|October 4, 2024
PubMed
Summary
This summary is machine-generated.

Understanding radical polarity is key to controlling chemical reactions. This study quantifies radical electrophilicity and nucleophilicity, creating an experimentally validated database to predict reactivity and improve synthetic outcomes.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Physical Chemistry

Background:

  • Radical intermediate polarity significantly influences reactivity and selectivity in chemical synthesis.
  • Predicting and quantifying this influence is crucial for reaction development.

Purpose of the Study:

  • To computationally calculate the electrophilicity/nucleophilicity of over 500 radicals.
  • To experimentally validate these calculated polarities for a diverse range of radical species.
  • To establish a predictive model correlating radical polarity with reactivity and selectivity.

Main Methods:

  • Density Functional Theory (DFT) calculations to determine electrophilicity/nucleophilicity (ω) for >500 radicals.
  • Experimental validation using competition experiments with >50 C-centered, N-centered, and O-centered radicals.
  • Correlation analysis between computed polarity and quantified relative reactivity (k_rel).

Main Results:

  • A comprehensive database of computed radical polarities for common synthetic intermediates.
  • Experimental validation confirmed high correlations between calculated polarity and measured reactivity.
  • A strong relationship was observed between electrophilicity (ω) and relative reactivity (k_rel), with small polarity changes yielding significant rate enhancements.

Conclusions:

  • The experimentally validated database enables accurate prediction of radical reactivity and selectivity.
  • Harnessing polarity-matched rate enhancement can optimize synthetic reaction development.
  • This resource will aid in troubleshooting and designing novel synthetic pathways.