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Related Concept Videos

Radical Formation: Addition00:47

Radical Formation: Addition

1.6K
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...
1.6K
Radical Formation: Elimination00:51

Radical Formation: Elimination

1.6K
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions...
1.6K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.2K
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...
2.2K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

1.4K
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...
1.4K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

1.7K
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...
1.7K
Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics01:32

Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics

2.0K
The anti-Markovnikov addition of hydrogen halides to an alkene is thermodynamically feasible only with HBr. The radical addition reaction with other hydrogen halides like HCl and HI is thermodynamically unfavorable.
2.0K

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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

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Roaming dynamics in radical addition-elimination reactions.

Baptiste Joalland1, Yuanyuan Shi1, Alexander Kamasah1

  • 1Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA.

Nature Communications
|June 7, 2014
PubMed
Summary

Chlorine atoms react with butenes via a roaming mechanism, not a standard transition state. This pathway involves the chlorine atom exploring the alkene before abstracting hydrogen, forming HCl.

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Area of Science:

  • Chemical kinetics
  • Reaction dynamics
  • Physical chemistry

Background:

  • Radical addition-elimination reactions are key for hydrocarbon transformations.
  • Gas-phase reactions involve transient intermediates, but mechanisms remain unclear.
  • Understanding reaction dynamics is crucial for chemical synthesis and atmospheric chemistry.

Purpose of the Study:

  • To elucidate the detailed mechanism and dynamics of chlorine atom reactions with butenes.
  • To investigate the role of transient intermediates and transition states in radical addition-elimination reactions.
  • To explore the phenomenon of roaming radical dynamics in bimolecular reactions.

Main Methods:

  • Computational studies of chlorine atom reactions with butenes.
  • Analysis of potential energy surfaces and reaction pathways.
  • Investigation of roaming dynamics and intermediate complex formation.

Main Results:

  • The Cl addition-HCl elimination pathway proceeds via an abstraction-like Cl-H-C geometry.
  • Roaming excursions of the chlorine atom from the initial adduct facilitate access to this geometry.
  • The alkene π cloud captures the chlorine atom, allowing exploration and reaction.
  • Bimolecular roaming reactions are observed, analogous to unimolecular roaming radical dynamics.

Conclusions:

  • The study reveals a novel roaming-mediated mechanism for radical addition-elimination reactions.
  • This finding challenges conventional transition state models for these transformations.
  • Roaming dynamics play a significant role in gas-phase chemical reactions involving unsaturated hydrocarbons.