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一電子酸化銅ビスフェノキシド複合体の電子構造と幾何学構造を定義する
Tim Storr1, Pratik Verma, Russell C Pratt
1Department of Chemistry, Stanford University, Stanford, California 94305, USA.
Journal of the American Chemical Society
|October 23, 2008
まとめ
銅複合体[CuSal](+) は金属ベースの酸化場所を示し,固体ではCu(III) を形成し,溶液中のCu(II) とCu(III) の間のスピン均衡を示します. リンガンド構造は,銅複合体の酸化部位に大きな影響を与える.
科学分野:
- 無機化学 無機化学とは
- 協調化化学について
- スペクトル顕微鏡検査です.
背景:
- 非無害な結合体を持つ金属複合体の電子構造は,それらの反応性を理解するために重要である.
- 金属ベースの酸化とリガンドベースの酸化を区別することは,協調化学における重要な課題です.
- サラン型リガンドを持つ銅複合体は,その多様な電子特性で知られている.
研究 の 目的:
- 酸化銅複合体の幾何学および電子構造を調査するために,[CuSal](+).
- 銅複合体の酸化場所 (金属対リガンド) を決定する.
- 銅-ビス-フェノキシド複合体の酸化部位におけるリガンド構造の影響を調査する.
主な方法:
- UV対NIRスペクトロスコピーは,UV対NIRスペクトロスコピーを用いて行われます.
- 磁気感受性の測定について
- 電気化学 電気化学について
- 共振ラーマン光譜法
- X線結晶グラフィーです.
- X線吸収スペクトロスコピーは,X線吸収スペクトロスコピーを用います.
- 密度関数理論 (DFT) の計算
主要な成果:
- 酸化した銅複合体[CuSal](+) は,固体状態において Cu(III) 種のみを形成する.
- 溶液中の[CuSal](+) は,Cu(II) -リガンド-ラジカルとCu(III) の形態の間の可逆スピン均衡を示している.
- ビス-イミネ-ビス-フェノラートリガンドはCu (III) の酸化状態を安定させ,調整変化なしにスピン均衡を促進します.
- 関連するテトラヒドロサレンのアナログである[CuSal (赤) ] (赤) +) は,温度不変のCu (II) -リガンド-ラジカル複合体として存在する.
結論:
- [CuSal](+) の酸化位置は主に金属基で,固体状態ではCu(III) を形成する.
- 溶液の研究は, [CuSal] (((+) のためのユニークなスピン均衡を明らかにし,Cu (((II) 根とCu (((III) の状態がほぼ同エネルギーであることを示しています.
- リガンドの設計は,銅複合体の酸化部位と電子的振る舞いを制御する上で重要な役割を果たします.
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