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

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

3.4K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
3.4K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

2.8K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
2.8K
Preparation of Diols and Pinacol Rearrangement01:57

Preparation of Diols and Pinacol Rearrangement

4.2K
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
4.2K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.7K
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...
2.7K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

2.5K
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...
2.5K
Radicals01:27

Radicals

731
Roots, often written as radicals, identify the quantity that must be raised to a specific exponent to produce a given value. A radical expression consists of two main components: the radicand, which is the value placed inside the root symbol, and the index, which indicates the degree of the root being taken. The notation n√a indicates the principal nth root of a. If n equals 2, the operation is the square root, while n = 3 defines the cube root. When n is even, a negative radicand does...
731

You might also read

Related Articles

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

Sort by
Same author

Reactive Intermediates and Unusual Molecules: 70 Years with Fascinating Chemistry.

Chemical record (New York, N.Y.)·2025
Same author

Mechanistic Insights into NO Releasing by Functionalized Carbon Quantum Dots: A DFT Study.

ACS omega·2025
Same author

Sydnone Photochemistry: Formation of Nitrenes.

The Journal of organic chemistry·2025
Same author

Melanin-Based Compounds as Low-Cost Sensors for Nitroaromatics: Theoretical Insights on Molecular Interactions and Optoelectronic Responses.

ACS omega·2025
Same author

The Gold-Maker of Animal Oil and Prussian Blue Fame - The Chemical and Medicinal Science Philosophy of Johann Conrad Dippel.

Chemical record (New York, N.Y.)·2025
Same author

The Sweet Spirits of the Mineral Acids: Diethyl Ether, Ethyl Nitrite, and Chloroethane. Late Medieval-Early Modern Organic Chemistry.

Chemical record (New York, N.Y.)·2024

Related Experiment Video

Updated: Feb 4, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
08:22

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Published on: August 6, 2018

7.3K

Phenylnitrene Radical Cation Rearrangements.

Didier Bégué1, Alain Dargelos1, Curt Wentrup2

  • 1CNRS/Université de Pau et des Pays de l'Adour/E2S UPPA , Institut des Sciences Analytiques et de Physicochimie pour l'Environnement et les Matériaux , UMR5254, 64000 Pau , France.

The Journal of Physical Chemistry. A
|October 10, 2018
PubMed
Summary
This summary is machine-generated.

Phenylnitrene radical cation undergoes ring expansion and opening reactions. These rearrangements are analogous to thermal and photochemical processes, offering insights into reactive intermediates.

More Related Videos

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
14:22

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

Published on: April 15, 2013

20.8K
Synthesis of Cationized Magnetoferritin for Ultra-fast Magnetization of Cells
10:23

Synthesis of Cationized Magnetoferritin for Ultra-fast Magnetization of Cells

Published on: December 13, 2016

10.4K

Related Experiment Videos

Last Updated: Feb 4, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
08:22

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Published on: August 6, 2018

7.3K
Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
14:22

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

Published on: April 15, 2013

20.8K
Synthesis of Cationized Magnetoferritin for Ultra-fast Magnetization of Cells
10:23

Synthesis of Cationized Magnetoferritin for Ultra-fast Magnetization of Cells

Published on: December 13, 2016

10.4K

Area of Science:

  • Computational Chemistry
  • Organic Chemistry
  • Reaction Mechanisms

Background:

  • Phenylnitrene radical cation is a key intermediate in various chemical reactions.
  • Understanding its electronic structure and reactivity is crucial for predicting reaction pathways.

Purpose of the Study:

  • Investigate the electronic structure of phenylnitrene radical cation.
  • Elucidate the rearrangement mechanisms, including ring expansion and opening.
  • Compare these rearrangements to known thermal and photochemical processes.

Main Methods:

  • Density Functional Theory (DFT) calculations.
  • Complete Active Space Perturbation Theory (CASPT2) with a (7,9) active space.
  • Analysis of electronic states, activation energies, and reaction pathways.

Main Results:

  • The lowest energy electronic state of phenylnitrene radical cation is identified as 2B2.
  • Ring expansion to 1-azacycloheptatetraene radical cation occurs with a 28 kcal/mol activation energy.
  • Interconversion pathways with pyridylcarbene radical cations via azacycloheptatetraenes were established with barriers <35 kcal/mol.

Conclusions:

  • Phenylnitrene radical cation exhibits diverse rearrangement pathways, including ring expansion, opening, and cyclization.
  • These complex rearrangements are analogous to established thermal and photochemical reactions.
  • The study provides a detailed computational understanding of these reactive intermediates.