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関連する概念動画

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.5K
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...
2.5K
Radical Formation: Addition00:47

Radical Formation: Addition

2.1K
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...
2.1K
Radical Formation: Overview01:03

Radical Formation: Overview

2.5K
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...
2.5K
Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

Woodward–Hoffmann Selection Rules and Microscopic Reversibility

3.6K
Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
3.6K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.5K
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...
2.5K
Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals01:17

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

3.1K
Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling interactions can occur between the spins of the unpaired electron and any neighboring spin-active nuclei. This hyperfine coupling results in hyperfine splitting, where the EPR signal is split into multiplets. The signals split into 2nI + 1 peaks, where n is the number of equivalent nuclei and I is the nuclear spin. These splitting patterns provide...
3.1K

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関連する実験動画

Updated: Dec 8, 2025

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

Published on: April 19, 2019

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鉄基スピンクロスオーバーによる有機ダイラディカル性質の可逆的な切り替え

Airi Kawamura1, Jiaze Xie1, Jan-Niklas Boyn1

  • 1Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.

Journal of the American Chemical Society
|September 19, 2020
PubMed
まとめ
この要約は機械生成です。

研究者は,無機のスピントランジションが有機のダイラジカル特性を制御する方法を示しています. テトラチアフルバレン-2,3,6,7-テトラチオラートリガンドを持つ二鉄複合体は,熱誘発のスピンクロスオーバーを示し,ダイラジカル特性を生成する.

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Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

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関連する実験動画

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Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
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科学分野:

  • 協調化学
  • オーガニックの電子機器
  • 材料科学

背景:

  • 有機ダイラジカルは稀ですが,様々な用途にユニークな性質を持っています.
  • 外部刺激でダイラジカルな性格をコントロールすることは,最近の研究の焦点です.

研究 の 目的:

  • 無機のスピン変換が 有機のダイラジカル性質を 調節できることを示すために
  • テトラチアフルバレン-2,3,6,7-テトラチオラート (TTFtt2-) リガンドを含む二鉄複合体を調査する.

主な方法:

  • UV対近赤外線,Mössbauer,NMR,およびEPRスペクトロスコピーを利用した.
  • マグネトメトリー,結晶学,そして高度な理論的計算を行いました.
  • 熱誘導されたFe中心のスピンクロスオーバーを調査した.

主要な成果:

  • Fe (II) を中心としたスピン・クロスオーバーは,TTFtt2-リガンドに有意なダイラジカル特性を誘発した.
  • ダイラジカルな性質は,縮小するTTFtt2-π多様性から生じる.
  • 理論的および実験的データは,ダイラジカルに対するシングレット基底状態を予測します.

結論:

  • 無機スピントランジションは,有機 dirradical 性格を制御するための新しい経路を提供します.
  • この研究は,ダイラジカル種とその刺激反応変調の理解を広げています.