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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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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 Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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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: Overview01:03

Radical Formation: Overview

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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:
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...
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Radical Formation: Addition00:47

Radical Formation: Addition

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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.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
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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.
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...
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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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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...
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Heteroatom-Based Diradical(oid)s.

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This review explores heteroatom-centered diradicaloids, evolving concepts from theoretical underpinnings to rational design strategies. It highlights their unique reactivity and applications in areas like small molecule activation.

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Area of Science:

  • Molecular main group chemistry
  • Theoretical chemistry

Background:

  • Heteroatom-centered diradicaloids have been studied for decades.
  • The field has shifted towards rational design for specific applications.

Purpose of the Study:

  • To review theoretical considerations of diradical and tetraradical concepts.
  • To highlight the rational design of diradicaloids based on theoretical insights.
  • To discuss heteroatom-centered diradical reactions and their applications.

Main Methods:

  • Theoretical considerations of diradical and tetraradical concepts.
  • Analysis of design principles including ligand choice, sterics, symmetry, electronics, and element choice.
  • Comparison of open-shell diradical reactivity with closed-shell reactions.
  • Review of spectroscopic properties and recent literature (last 10 years).

Main Results:

  • Diradicaloid design principles have been elucidated.
  • Heteroatom-centered diradical reactions exhibit distinct stepwise reactivity compared to concerted closed-shell reactions.
  • Diradicaloids show potential in applications such as small molecule activation and molecular switches.

Conclusions:

  • A rational understanding of diradicaloid reactivity is achieved through design considerations and reactivity comparisons.
  • Recent advancements in heteroatom-centered diradicaloids and tetraradicaloids have expanded their scope.
  • Diradicaloids represent a versatile class of compounds with significant application potential.