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Radical Reactivity: Overview01:11

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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 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...
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Radical Reactivity: Nucleophilic Radicals01:16

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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...
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Radical Formation: Addition00:47

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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.
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Radical Formation: Overview01:03

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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:
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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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.
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Imaging Frontside and Backside Attack in Radical Ion-Molecule Reactive Scattering.

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  • 1Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstrasse 25/3, 6020 Innsbruck, Austria.

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Atomic oxygen anions (O) react with methyl iodide (CH3I), forming iodide (I) and iodoxyl (IO) products. The study reveals distinct reaction pathways and scattering dynamics for backside and frontside attacks.

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Area of Science:

  • Chemical Dynamics
  • Physical Chemistry
  • Reaction Mechanisms

Background:

  • Methyl iodide (CH3I) is a key molecule in atmospheric chemistry.
  • Radical ion-molecule reactions are fundamental to understanding chemical processes.
  • Atomic oxygen anions (O) are reactive species with significant chemical potential.

Purpose of the Study:

  • To investigate the reactive scattering of methyl iodide with atomic oxygen anions.
  • To elucidate the stereodynamics of the O + CH3I reaction.
  • To determine the product branching ratios and scattering distributions.

Main Methods:

  • Crossed-beam velocity map imaging experiments.
  • Quantum chemical calculations.
  • Energy-dependent scattering measurements (0.3–2.0 eV).

Main Results:

  • Iodide (I) is the predominant product, formed via three distinct pathways.
  • Backside attack leads to indirect, forward, and sideways scattered I products through a hydrogen-bonded complex.
  • Frontside attack yields iodoxyl (IO) products, which can further dissociate to I + O at higher energies.

Conclusions:

  • The reaction dynamics are highly dependent on the angle of attack of O on CH3I.
  • Stereoselective scattering provides insights into the reaction mechanism.
  • Product branching and dissociation pathways are influenced by collision energy.