フェニルスルフィニルラジカル:ガス相生成,光異体化,酸化
Jian Xu1, Zhuang Wu1, Huabin Wan1
1College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
Journal of the American Chemical Society
|July 11, 2018
まとめ
フェニルスルフィニルラジカルは初めてガス相で生成された. 紫外線照射により,これらのラジカルは新しいオクサチルラジカルに異体化し,さらに変化し,様々なラジカル種を生成する.
科学分野:
- * 物理化学
- * 有機化学
- * 顕微鏡検査
背景:
- * アリルスルフィニルラジカルは,硫化物化学における重要な中間物質である.
- * フェニルスルフィニルラジカル (PhSO•) の生成と光化学的振る舞いは,以前はガス段階では研究されていなかった.
研究 の 目的:
- * ガス相で初めてフェニルシルフィニル基 (PhSO•) を生成する.
- * PhSO•とその誘導体の光化学的異体化と反応を調査する.
- * 新種の中間基質の特徴を,スペクトロスコーピカルと計算的方法を用いて特定する.
主な方法:
- * PhSO•を生成するために,高真空のフラッシュ熱分解で PhS (R = CF3 と Cl) を ~1000 K で生成する.
- * 低温マトリックス (2.8K) のラジカルに対する紫外線照射 (365nmと193nm).
- * PhSO•の分子酸素とのガス相反応
- * IRとUVのスペクトロスコピーを用いた中間物質の識別
- * 量子化学計算 (B3LYP/def2-TZVPPとUCCSD(T) / aug-cc-pV(D+d) Z) について
主要な成果:
- * ガス相でフェニルシルフィニル基 (PhSO•) が成功して生成された.
- * PhSO•は紫外線照射によってオキシチル基 (PhOS•) に同化する.
- * PhOS•はさらに2ヒドロキシフェニルチル基に異体化し,リング開きを経てチオケトケテン基を形成する.
- * O2との反応は,フェニル基 (Ph•) とOSOO,またはフェノキシ基 (PhO•) とSO2を生成する.
- * 顕微鏡および計算データにより,観測されたすべての中間物質の識別が可能です.
結論:
- * この研究は,フェニルスルフィニル基の最初のガス相生成を報告している.
- スルフィニルとオクサチルラジカルのイソメリゼーションとリング開封を含む新しい光化学経路が解明されました.
- * この発見は,硫黄酸化物質から派生した急性物質の反応性と光化学に関する洞察を提供します.
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