安定したN-ヘテロサイクリックシリレンの急性反応: EPR研究とDFT計算
Boris Tumanskii1, Pauline Pine, Yitzhak Apeloig
1Department 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
|June 24, 2004
まとめ
安定したシリエレンは,根源と反応してアダクトを形成します. これらのアダクトのペア化されていない電子は,EPRスペクトロスコーピーによって示されたように,シリコンを含むリング全体に分散しています.
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
- スペクトル顕微鏡検査です.
背景:
- 安定したシリエレンは,反応性シリコンの中間物質である.
- フリーラジカルは,非常に反応性の高い種です.
研究 の 目的:
- 安定したシリレンが様々な自由根源と反応する過程を研究する.
- 電子パラマグネティック共振 (EPR) スペクトロスコーピーを用いて,結果として発生した根付加を特徴付ける.
主な方法:
- 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylideneの反応は,TEMPO,Hg[P(O) ((OPri) ]2, (CO) 3CpM-MCp ((CO) 3 (M = W,Mo), (CO) 5Re-Re ((CO) 5) とトゥーレンで起こっています.
- EPR光譜を用いた反応産物の分析.
主要な成果:
- シリレンと試験されたすべての根源との反応から,安定した根源アダクトの形成.
- EPRスペクトルは,ペア化されていない電子が,シリコンを含む5つ組のリングの上に非局所化されていることを明らかにしました.
結論:
- 安定したシライレンは,フリーラジカルを効果的に捕まえて,持続的なラジカルアダクトを形成します.
- これらのアダクトの電子構造は,非対の電子がシリレンフレーム上に有意な移転を特徴としています.
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