Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

2.0K
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...
2.0K
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

4.2K
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...
4.2K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
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...
2.1K
Radical Reactivity: Concentration Effects01:20

Radical Reactivity: Concentration Effects

1.5K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
1.5K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

1.8K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.8K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.2K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.2K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Development of a Core Outcome Domain Set for Facial Aging.

JAMA dermatology·2026
Same author

Novel 1550-nm Nonablative Resurfacing Laser With Focal Point Technology Improves Fine Lines and Wrinkles With High Energy Delivery.

Dermatologic surgery : official publication for American Society for Dermatologic Surgery [et al.]·2026
Same author

Selective Electrochemical Defluorinative Hydroxymethylation toward Difluoro-Substituted Alcohol Building Blocks.

Organic letters·2026
Same author

Endovascular management of femoral artery duplication with a proposed anatomical classification.

Surgical and radiologic anatomy : SRA·2026
Same author

Interplay between ligand field strength and the nephelauxetic effect in chromium(iii) complexes with anionic amido ligands.

Chemical science·2026
Same author

Flash Communication: (Ph<sub>3</sub>P)<sub>2</sub>N<sub>2</sub>Aza-Wittig Reagent for Metal Carbonyls.

Organometallics·2026
Same journal

Efficient Syngas Photoproduction Enabled by Electronic Engineering of Co-Immobilized Imine COFs.

Angewandte Chemie (International ed. in English)·2026
Same journal

Pathway Controlled Phase Separation of Minimal Building Blocks Utilizing a Dissociative Chemical Transformation.

Angewandte Chemie (International ed. in English)·2026
Same journal

Interaction Hierarchy and Polymorphic Structure-Property Dynamics in Luminescent Molecular Crystals.

Angewandte Chemie (International ed. in English)·2026
Same journal

The Role of Zn-Hf Site Proximity and Oxygen Vacancies for Methanol Formation Over ZnHfO<sub>x</sub> Catalysts Under CO<sub>2</sub> Hydrogenation Conditions.

Angewandte Chemie (International ed. in English)·2026
Same journal

Breaking the Linear Scaling Relationship: Bioinspired Electronic Coupling in S-Bridged Fe-Fe Dual Sites for Efficient Oxygen Reduction.

Angewandte Chemie (International ed. in English)·2026
Same journal

Programming Bio-Bio Electronic Interfaces for Light-Driven Interspecies Electron Transfer.

Angewandte Chemie (International ed. in English)·2026
See all related articles

Related Experiment Video

Updated: Sep 5, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
10:44

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Published on: April 19, 2019

11.0K

Gauging Radical Stabilization with Carbenes.

Kevin Breitwieser1, Hilke Bahmann2, Robert Weiss3

  • 1Coordination Chemistry, Saarland University, Campus C4.1, 66123, Saarbrücken, Germany.

Angewandte Chemie (International Ed. in English)
|July 7, 2022
PubMed
Summary
This summary is machine-generated.

Designing effective radical-stabilizing C-donor ligands is now possible. This study reveals that carbene ligands stabilize radicals through frontier orbital interactions, offering new insights into N-heterocyclic carbene chemistry.

Keywords:
CarbenesDensity Functional CalculationsMolecular OrbitalsN-Heterocyclic CarbeneRadicals

More Related Videos

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
10:34

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow

Published on: April 24, 2014

10.9K
Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
14:07

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Published on: October 3, 2014

13.7K

Related Experiment Videos

Last Updated: Sep 5, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
10:44

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Published on: April 19, 2019

11.0K
Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
10:34

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow

Published on: April 24, 2014

10.9K
Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
14:07

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Published on: October 3, 2014

13.7K

Area of Science:

  • Organometallic Chemistry
  • Ligand Design
  • Radical Stabilization

Background:

  • Carbenes, particularly N-heterocyclic carbene (NHC) ligands, are crucial for stabilizing open-shell transition metal complexes and organic radicals.
  • The precise factors governing a carbene's ability to stabilize radicals are not well understood, hindering the rational design of novel C-donor ligands.
  • Existing knowledge often overlooks the significant π-donor effects of NHC ligands in radical stabilization.

Purpose of the Study:

  • To elucidate the fundamental principles governing radical stabilization by C-donor ligands.
  • To establish a predictive model for designing ligands that effectively stabilize radicals.
  • To re-evaluate the role of π-donation in N-heterocyclic carbene chemistry.

Main Methods:

  • Investigated a diverse range of experimentally studied C-donor ligands with established electronic properties.
  • Applied a captodative frontier orbital description to analyze radical stabilization mechanisms.
  • Evaluated the thermodynamic stability of covalent radicals in main group and transition metal carbene complexes.

Main Results:

  • Demonstrated that radical stabilization is governed by frontier orbital interactions, specifically π-donation to and from the carbene ligand.
  • Showcased the significant contribution of π-donor effects in NHC ligands, challenging previous assumptions.
  • Provided a framework for intuitively predicting the stability of covalent radicals and quantifying redox non-innocence.

Conclusions:

  • The captodative frontier orbital model offers a new perspective on carbene ligand design for radical stabilization.
  • This research enables the rational design of C-donor ligands with tailored radical-stabilizing capabilities.
  • The findings have implications for understanding and controlling the reactivity of transition metal complexes and organic radicals.