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予期せぬB/Alトランセレメント Rhピンサー複合体内

  • 0Department of Chemistry, Texas A&M University, 3255 TAMU, College Station, Texas 77842, United States.
Journal of the American Chemical Society +

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2020年12月2日

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2020年12月2日

PubMedで要約を見る

まとめ

この要約は機械生成です。

研究者はアルミニウムやボロン中心でロジウムピンチャー複合体を合成した. 予期せぬB/Al転移は,アルミニウム部位を改変しようとすると発生し,代わりにボロン複合体を生成した.

科学分野

  • 有機金属化学
  • 協調化学
  • メイングループ 化学

背景

  • ピンサー複合体は,その三角調節により,ユニークな反応性を提供します.
  • アルミニウムとボロンは,それぞれメイングループと有機金属化学の重要な元素です.
  • 低座標の主なグループ要素の安定化と反応性を理解することは極めて重要です.

研究 の 目的

  • bis (N-ピロリル) アルミニル (PAlP) とボリル (PBP) ユニットを含む新しいロジウムピンカー複合体を合成し,特徴づけること.
  • PAlPロジウム複合体のアルミニル部位の反応性を調査する.
  • 3つの座標のアルミニウムセンターへのアクセス方法を探求する.

主な方法

  • PAlPとPBPロジウムジカルボニル複合体の合成
  • (PAl<sup>py</sup>P) Rh(CO) <sub>2</sub>におけるアルミニル部位を安定させるためのピリジンの調整.
  • BF<sub>3</sub>·Et<sub>2</sub>OとB(C<sub>6</sub>F<sub>5</sub>) <sub>3</sub>を用いたルイス酸媒介のピリジン抽出を含む反応.

主要な成果

  • ピリジンによって安定した4座標のアルミニウム中心で (PAl<sup>py</sup>P) Rh ((CO) <sub>2</sub>の合成が成功しました.
  • BF<sub>3</sub>·Et<sub>2</sub>Oで治療した際に予期せぬB/ Al転移が起こり, (PBP) Rh<sub>CO<sub>2</sub>複合体を形成し,ピンサー構造を保ちました.
  • B ((C<sub>6</sub>F<sub>5</sub>) <sub>3</sub>を用いたピリジン抽出の試みは,イソカルボニルブリッジングによるPAlP複合体の二元化につながった.

結論

  • ピリジンの調整は,ロジウムピンサー複合体の4座標アルミニルサイトを安定させるのに有効である.
  • ルイス酸媒介反応は予期せぬB/Al転移を引き起こし,ボリル複合体に対する代替経路を提供する.
  • アルミニルピンサー複合体の反応性は抽出剤に敏感であり,特定の条件下で二分化につながる.

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