Jove
Visualize
お問い合わせ
JoVE
x logofacebook logolinkedin logoyoutube logo
JoVEについて
概要リーダーシップブログJoVEヘルプセンター
著者向け
出版プロセス編集委員会範囲と方針査読よくある質問投稿
図書館員向け
推薦の声購読アクセスリソース図書館諮問委員会よくある質問
研究
JoVE JournalMethods CollectionsJoVE Encyclopedia of Experimentsアーカイブ
教育
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab Manual教員リソースセンター教員サイト
利用規約
プライバシーポリシー
ポリシー

関連する概念動画

Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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 low‐energy SOMO, which interacts...
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic factors, steric factors also account...
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...

こちらも読む

関連記事

共著者、ジャーナル、引用グラフによってこの研究に関連する記事。

並び替え
Same author

Synthesis of the First Isolable Geminal 1,1-Dilithiostannane and Its Intriguing Structural Diversity.

Angewandte Chemie (International ed. in English)·2025
Same author

The First Planar, Not Twisted, Distannene - A Structural Alkene Analog. Synthesis, Isolation and X-ray Crystallography Characterization.

Chemistry (Weinheim an der Bergstrasse, Germany)·2023
Same author

Robert C. West (1928-2022): A Giant in Organosilicon Chemistry, Cosmopolitan, Mountain Climber and Pilot.

Angewandte Chemie (International ed. in English)·2023
Same author

Facile Synthesis of an Octagermacubane with Two Three-Coordinate Germanium(0) Atoms and its Unique Radical Anion.

Angewandte Chemie (International ed. in English)·2023
Same author

Multimodal Reactivity of N-H Bonds in Triazanes and Isolation of a Triazinyl Radical.

Journal of the American Chemical Society·2022
Same author

Geometrically constrained square pyramidal phosphoranide.

Chemical science·2022

関連する実験動画

Updated: Jun 20, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

隔離可能な光反応性ポリシリル基素.

Gregory Molev1, Boris Tumanskii, Dennis Sheberla

  • 1Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.

Journal of the American Chemical Society
|September 3, 2009
PubMed
まとめ
この要約は機械生成です。

安定したシリルラジカルは,新しい1ステップ法を使用して合成されました. これらのシリコンラジカルは独特の光化学的性質を示し,あるタイプはシランとディシレンに分解し,他のタイプは放射線で水素抽出を受けます.

さらに関連する動画

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
09:17

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Published on: January 30, 2015

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
08:12

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

Published on: December 16, 2022

関連する実験動画

Last Updated: Jun 20, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
09:17

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Published on: January 30, 2015

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
08:12

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

Published on: December 16, 2022

科学分野:

  • オーガノシリコン化学 化学
  • ラジカル・ケミストリー (Radical Chemistry) とは
  • フォトケミストリー フォトケミストリー

背景:

  • 安定したシリルラジカルは,シリコン化学における重要な中間物質である.
  • シリルラジカルを合成する以前の方法は限られていた.
  • シリル基の反応性と光化学を理解することは,新しい合成経路の開発に不可欠です.

研究 の 目的:

  • 安定したシリル基を合成するための一般的で効率的な1段階の方法を開発する.
  • 新しく合成されたシリルラジカルの構造と性質を特徴付ける.
  • これらのシリルラジカルの光化学的行動と反応機構を調査する.

主な方法:

  • シリル置換のジクロロシランとヒクサンのリチオシランの反応.
  • X線結晶学を含むシリル基の分離と完全な特徴付け.
  • 光化学放射線実験 (λ > 400 nm) とDFT計算.

主要な成果:

  • 新しい1段階合成により,安定したシリルラジカルのみが得られます.
  • 2つのシリル基 (t-Bu(2)MeSi) (((2)HSi(t-Bu(2)MeSi) (((2)Si* (1) と (t-Bu(2)MeSi) (((3)Si* (2) が分離され,特徴づけられました.
  • ラジカル1は光分解によりシランとディシレンに分解し,ラジカル2は光安定性を示しているが,放射線で水素を抽象化している.
  • DFTの計算と照射データは,SOMO-1 → SOMOの刺激が光反応性に影響することを示しています.

結論:

  • 開発された1段階の方法は,多様な安定したシリル基を合成するための一般的なアプローチです.
  • シリル基は,電子構造によって影響を受け,明確な光化学反応性を示す.
  • フォトリアクティビティは,特定の電子刺激と関連しており,制御された化学変換を可能にします.