銅の伝説 (III)
Ida M DiMucci1, James T Lukens1, Sudipta Chatterjee1
1Department of Chemistry and Chemical Biology , Cornell University , Baker Laboratory, 162 Sciences Drive , Ithaca , New York 14853 , United States.
Journal of the American Chemical Society
|November 12, 2019
まとめ
高値銅 (Cu) 複合体は,高値共性金属-リガンド結合を示し,酸化状態の割り当てを複雑にする. 電子の穴は銅ではなく,リガンドに存在し,従来のCu (I) /Cu (III) 酸化還元記述に異議を唱える.
科学分野:
- 無機化学
- コンピュータ化学
- スペクトロスコーピー
背景:
- 銅の酸化状態を理解することは,触媒化にとって極めて重要です.
- 高価性銅の種は,様々な化学的変異に関与しています.
- 銅複合体における酸化状態の正確な割り当ては困難である.
研究 の 目的:
- 様々な酸化状態における銅複合体の電子構造を調査する.
- 高値銅種における金属・リガンド結合の性質を明らかにする.
- 銅の酸化還元過程の伝統的な説明を再評価する.
主な方法:
- マルチエッジのX線吸収光譜法 (XAS) が電子構造を検知するために使用された.
- 密度関数理論 (DFT) の計算は,実験結果のモデル化と検証に使用された.
- X線吸収データの共相性分析が行われました.
主要な成果:
- 高値銅 (Cu(III)) 複合体は,有意なメタル-リガンド共性性を表している.
- Cu K-エッジとL2,3-エッジのスペクトルは,共振結合によって複雑化した特徴を示している.
- 正式にCu ((III) 種は,LUMOのCu (d) 文字を減少させた.
- 電子の穴の特徴は,銅のみではなく,サポートリガンドにも位置する.
結論:
- 公式のCu (III) 種に対する物理的なd8記述は不正確である.
- 銅は酸化能力が限られており,電子の穴はリガンドに存在する.
- この研究は,正規のCu (III) 種が酸化還元過程における反応性について,別の説明を提供している.
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