Fe ((CO) 5リガンドを含むヘテロメタリック銀-鉄複合体
Guocang Wang1, Yavuz S Ceylan2, Thomas R Cundari2
1Department of Chemistry and Biochemistry, The University of Texas at Arlington , Arlington, Texas 76019, United States.
Journal of the American Chemical Society
|September 29, 2017
まとめ
鉄 ((0) ペンタカーボニルはリガンドとして作用し,新しい異金属銀-Fe ((CO)) 5複合体を形成する. これらの研究は,Ag-Fe結合の性質と協調化学における操作を明らかにする.
科学分野:
- 有機金属化学
- 協調化学
- 無機化学
背景:
- 鉄 ((0) ペンタカルボニル (Fe ((CO) 5) はよく知られている有機金属化合物である.
- 通常,Fe ((CO) 5) は様々なリガンドとカーボニル異位反応を起こします.
- この研究では,Fe ((CO) 5) のリガンドとしての役割はあまり一般的ではない.
研究 の 目的:
- 結合体としての鉄 ((0) ペンタカルボニルの調整行動を調査する.
- 銀とFe (CO) 5を含む新しい異金属複合体を合成し,特徴づけること.
- これらのユニークな金属対金属相互作用の 構造的,結合的,電子的性質を調査する.
主な方法:
- Fe(CO) 5と銀塩 (AgSbF6,Ag[B{3,5-(CF3) 2C6H3}4) の反応
- ヘテロメタリックとヘトロトリメタリックの合成
- X線結晶学,光譜法 (IR) および計算分析を用いた特徴化.
主要な成果:
- [μ-H2O]AgFe (CO) ]2[SbF6]2および[B{3,5-(CF3) 2C6H3}4]AgFe (CO) 5のような複合体のヘテロメタリック{Ag-Fe (CO) 5}+断片の形成
- Ag-Fe結合を維持しながら,銀の調整球を操作する.
- Fe-Ag結合距離は2.5833 ((4)) から2.6219 ((5) Åまであり,主に電荷移転によるイオン性である.
- 青色シフトした ν̅(CO) 帯は,銀の調整時にFe→COのバックボンドが減少したことを示している.
結論:
- Fe ((CO) 5はAg-Fe結合を形成するリガンドとして効果的に作用する.
- Ag-Fe結合は静電相互作用と部分電荷移転によって特徴付けられる.
- 銀への調整はFe (CO) 5リガンドの電子特性を大きく変化させる.
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