フェニルボリレンと二酸化窒素と一酸化炭素の光反応
Klara Edel1, Matthias Krieg1, Dirk Grote2
1Institut für Organische Chemie, Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Journal of the American Chemical Society
|October 11, 2017
まとめ
反応性のある中間物質であるフェニルボリレンは,光譜を用いて研究された. 窒素と逆行的に反応し,一酸化炭素と逆行的に反応し,ダイアゾアルカンとケテンの新しいボロン類を作ります.
科学分野:
- 有機金属化学
- スペクトロスコーピー
- 写真化学
背景:
- ボラン (BR3) は,2つの結合パートナーの正式な除去でボリレン (RB) を得ることができる.
- ボリレンは様々な化学反応に関与する反応性中間物質である.
- フェニルボリレン (PhB) は,フェニルジアジドボランからダイナトロゲン挤出で合成される.
研究 の 目的:
- フェニルボリレン (PhB) の性質と反応性を調査する.
- フェニルボリレンとその反応産物を光譜法で特徴づける.
- N2やCOのような小さな分子とフェニルボリレンの光化学反応を調査する.
主な方法:
- マトリックス隔離 低温条件下
- 特徴付けのためのUV/vis,IR,ESRスペクトロシー.
- 構造分析のための密度関数理論 (DFT) 計算.
主要な成果:
- フェニルボリレンは375 nm (S0 → S2) で吸収帯を示し,518 nm (S0 → S1) で弱い帯を示した.
- フェニルボリレンはN2と逆転し,光化学的条件下でCOと不可逆的に反応した.
- PhBNNとPhBCOは,DFTによって確認された三重の電子基底状態と線形構造を持っています.
結論:
- フェニルボリレンには,N2とCOに対する電気反応性がある.
- この研究は,ディアゾアルカンとケテンのボロン類の最初の例を示している.
- フェニルボリレンの反応性が強調され,合成前駆体としての可能性が示されています.
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