中性リガンドプラットフォームを持つ八面体鉄 (V) -ニトリド種の生成,スペクトル,および化学的特徴
Gerard Sabenya1, Laura Lázaro1, Ilaria Gamba1
1Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona , Campus Montilivi, E17071 Girona, Catalonia, Spain.
Journal of the American Chemical Society
|June 10, 2017
まとめ
研究者らは,新しい鉄 ((V) ニトリド複合体,FeV(N) ((MePy2tacn) 2+を合成し,特徴づけました. この非常に反応性の高い種は 冷凍温度で安定し 新しい化学的変換を可能にする強力な酸化剤として作用します
科学分野:
- 無機化学
- 有機金属化学
- 材料科学
背景:
- 高価鉄ニトリド種は稀で,合成し特徴づけるのは難しい.
- 電子構造と反応性を理解することは,触媒と生物無機化学にとって極めて重要です.
- 以前の研究は,カチオンまたはアニオン性鉄ニトリド複合体に焦点を当てていた.
研究 の 目的:
- 新しい中性鉄 ((V) ニトリド複合体を合成し,特徴づけること.
- 鉄酸ナトリドの電子構造と結合を調査する
- 酸化剤としての鉄 (V) ニトリド種の反応性を調べる.
主な方法:
- 鉄 (III) アジド前駆体複合体の合成と特徴付け [FeIII(N3) ] (MePy2tacn) ] (PF6) 2
- 鉄を生成する前駆物の光分解 (V) ニトリド種 [FeV(N) ((MePy2tacn) ]2+
- 顕微鏡 (Mössbauer,EPR,FT-IR,X線吸収) と構造 (X線微分) 分析
- 計算研究 (密度関数理論)
主要な成果:
- 弱いFe-N3結合を持つ低スピン (S = 1/2) 鉄(III) アジド複合体の特徴
- 光分解による低スピン (S = 1/2) の鉄ナトリドの生成.
- 鉄 ((V) ニトリド種は短いFe-N結合 (1.64 Å) を表しており,冷凍温度でのみ安定している.
- 鉄 ((V) ニトリド複合体は,オレフィン,硫化物,C−H結合と反応する強力な2電子酸化剤として作用する.
結論:
- ニュートラルリガンドフレームワークによって安定した最初の八面体鉄のニトリド種が準備され,特徴づけられました.
- この鉄 ((V) ニトリド複合体は,新しい化学的変換を促進する重要な酸化能力を示しています.
- この研究は,光学的に,化学的に特徴づけられた高価鉄種の限られた既知の例を拡張します.
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