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Related Concept Videos

Radical Formation: Addition00:47

Radical Formation: Addition

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 unpaired...
Radical Formation: Overview01:03

Radical Formation: Overview

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 latter, also known...
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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 molecule. These three...
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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...
Radical Formation: Homolysis00:54

Radical Formation: Homolysis

A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
Radical Formation: Abstraction00:47

Radical Formation: Abstraction

The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...

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Related Experiment Video

Updated: May 28, 2026

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

Charge shift bonding concept in radical π-dimers.

Yong-Hui Tian1, Miklos Kertesz

  • 1Department of Chemistry, Georgetown University, 37th & O Streets NW, Washington, DC 20057-1227, USA.

The Journal of Physical Chemistry. A
|October 26, 2011
PubMed
Summary

Radical π-dimers exhibit charge shift (CS) bonding, similar to lone pairs in molecules like F(2). This CS bonding concept explains intermolecular interactions in π-stacking radical dimers, revealing a novel application of the lone pair bond weakening effect.

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Area of Science:

  • Chemical Bonding Theory
  • Quantum Chemistry
  • Supramolecular Chemistry

Background:

  • The charge shift (CS) bonding concept explains unusual sigma-bond features in molecules with lone pairs.
  • Radical π-dimers, particularly those involved in π-stacking, present unique intermolecular bonding characteristics.

Purpose of the Study:

  • To investigate pancake bonding in radical π-dimers through the lens of charge shift (CS) bonding.
  • To explore the role of nonbonding and slightly bonding π-electron pairs in these dimers.
  • To extend the CS bonding concept to a new class of molecules.

Main Methods:

  • Utilized computational evidence and theoretical arguments.
  • Employed the tetracyanoethylene anion dimer ([TCNE](2)(2-)) as a model system.
  • Performed calculations including selected intrapair excitations of SOMO-SOMO bonding and nonbonding π-orbitals, compared to CAS(2,2) calculations.

Main Results:

  • Pancake bonding in radical π-dimers demonstrates features consistent with CS bonding.
  • The overlap of singly occupied molecular orbitals (SOMOs) is crucial for intermolecular bonding in these dimers.
  • Significant binding contributions were recovered by including specific excitations, supporting the CS bonding analogy.

Conclusions:

  • The CS bonding concept effectively captures essential features of intermolecular bonding in radical π-dimers.
  • This study establishes an analogy between pancake bonded radical π-dimers and other CS bonded molecules.
  • A novel application of the lone pair bond weakening effect (LPBWE) was identified, where doubly occupied π-orbitals mimic lone pairs.