二価から五価の鉄イミド複合体と,N-C結合割れによるFe (V) ニトリド
Martin Keilwerth1, Weiqing Mao1, Sergio A V Jannuzzi2
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 1, 91058 Erlangen, Germany.
Journal of the American Chemical Society
|December 30, 2022
まとめ
研究者は新しいリガンドを使用して鉄イミド複合体を合成し,特徴づけ,多様な電子構造と反応性を明らかにした. これらの研究は,中から高価鉄の化学と窒素移転反応の洞察を提供します.
科学分野:
- 有機金属化学
- 無機化学
- カタリシス
背景:
- 終末鉄イミド複合体は,金属触媒による窒素移転反応における重要な中間物質である.
- 多用途のモデル化合物の開発は,それらの反応性を理解するために不可欠です.
- N-アンカーされたトリス-NHCケラティングリガンドであるTIMMNMesは,そのような複合体を合成するための新しいプラットフォームを提供します.
研究 の 目的:
- 中高値の鉄アルキルイミド複合体を合成し,比較する.
- これらの複合体の電子構造と反応性を調査する.
- Fe ((V) イミドの中間物質をFe ((V) ニトリド複合物に変換することを研究する.
主な方法:
- TIMMNMesリガンドと1-アダマンチルアジドを用いた鉄イミド複合体の合成
- 酸化状態IIからVの複合体へのアクセスのための段階的な化学的還元と酸化.
- シングルクリスタルX線 difraktion,SQUID磁化,電気化学,Mössbauer,IR,UV/vis,NMR,EPR,X線吸収スペクトロスコピーによる特徴付け
- 補完的な量子化学計算をする
主要な成果:
- 低スピンの鉄アダマンチルイミド (TIMMNMes) [FeNAd) ]0,1+,2+,3+ (2-5) の同構造連鎖の合成に成功した.
- 不安定なFe ((V)) アダマンチルイミドの中間物質が,N-C結合の割れによって分離可能なFe ((V)) ニトリド複合体 (6) に変換される.
- 安定したFe ((V)) エチルイミドを含む類似のエチルイミド複合体の合成,ニトリドを誘導する.
- 反応性と相関する多様な電子構造を明らかにする詳細な特徴.
結論:
- TIMMNMesリガンドは,様々な鉄イミドおよびニトリド複合体の合成を容易にする.
- 鉄イミド複合体の電子構造は,その反応性に大きく影響する.
- この研究は,高価鉄イミド複合体の基本的な化学と,窒素移転反応におけるその可能性に関する貴重な洞察を提供します.
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