グループ10のトランジション金属-炭素結合に"非観察者"トリコーディネートリンガンドをエンタルピー制御で挿入
Seung Jun Hwang1, Akira Tanushi2, Alexander T Radosevich2
1Department of Chemistry, POSTECH, Pohang 37673, Republic of Korea.
Journal of the American Chemical Society
|December 11, 2020
まとめ
研究者らは,ニッケルとパラジウム複合体の金属炭素結合にリン酸リンゴを挿入し,新しいメチルメタロフォスフォラン化合物を形成しました. プラチナ複合体は異なる反応性を示し,金属-炭素結合の強さの周期的な傾向を強調した.
科学分野:
- 有機金属化学
- 協調化学
- リン化学
背景:
- 遅い移行期の金属と炭素の結合は,触媒作用において極めて重要です.
- リン基は金属複合体の安定化に重要な役割を果たします.
- 金属-炭素結合へのリガンド挿入の理解は,反応性を告げる.
研究 の 目的:
- グループ10の金属と炭素の結合に新しいP^Pケレーティングリガンドの挿入を調査する.
- 新しいメチルメタロフォスフォラン化合物を合成し特徴づけること.
- ニッケル,パラジウム,プラチナの複合体の 異なる反応性を調べるため
主な方法:
- 非三角性リン酸 (P ((III)) トライアミド部分を含むP^Pケラティングリガンド (L1) の合成.
- グループ10の金属複合体 (Ni,Pd,Pt) とのL1の金属化反応
- 合成された化合物の光譜 (NMR,X線結晶学) 特性.
主要な成果:
- 安定したメチルメタロフォスファランを生成する Ni と Pd 複合体の金属メチル結合に非三角形の位をうまく挿入する.
- これらの新しいメチルメタロフォスフォラン化合物の特徴.
- メタロフォスフォランではなくビスフォスフィンケラートを形成するPt (II) 複合体との異なる反応性の観察.
結論:
- この研究は,NiとPdの遅い金属-炭素結合に三座標のリンガンドを挿入する可能性を実証している.
- グループ10内の異なる反応性は,金属-炭素結合エンタルピーの周期的な変化に起因する.
- この研究は,有機金属化学のためのリガンド設計の範囲を拡大する.
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