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還元された鉄のピンチャー複合体へのアリルおよびアルキルハリドの酸化添加

Stephan M Rummelt¹, Paul O Peterson¹, Hongyu Zhong¹

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society

|April 8, 2021

まとめ

鉄複合体は,アリルおよびアルキルハリドで2電子酸化添加を受けます. この研究は,特定の鉄二酸化窒素複合体の反応性を実証し,C ((sp2) -XとC ((sp3) -X結合裂解の反応経路の洞察を示している.

科学分野:

有機金属化学
無機化学
キャタリシス

背景:

鉄複合体は触媒に不可欠ですが,有機ハライドとの反応性はさらに理解する必要があります.
酸化添加メカニズムの理解は,新しい合成方法論の開発の鍵です.

研究の目的:

アリルとアルキルハリドの2電子酸化加えを,減少した鉄二酸化窒素複合体に調査する.
これらの変換の反応経路と運動を明らかにする.

主な方法:

(3,5-Me2MesCNC) Fe ((N2) 2) とアリルおよびアルキルハリドの反応
相対的な反応率を決定する競争実験.
反応産物の分析とメカニズム研究 (例えば,レジッククロック,同位体標識)

主要な成果:

イオドベンゼンとブロムベンゼンの急速な酸化添加により,Fe (II) 製品が形成される.
アリルハリドの既定反応順:I > Br > Cl
アルキルハリド添加物の中間基の証拠で,それぞれC ((sp2) -XとC ((sp3) -Xの結合割れのための協調したおよび段階的な経路が実証されています.

結論:

鉄二酸化窒素複合体は,アリルとアルキルハリドの両方で効率的に酸化される.
反応経路はC ((sp2) -XとC ((sp3) -Xの結合に異なっており,後者は中間基を含む.
この研究は,鉄媒介によるハロゲン活性化に関する貴重な力学的な洞察を提供します.

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