Dioxygen activation and catalysis around ambient temperature is a long-standing challenge in chemistry. Inspired by the significant roles of the hydrogen bond network in dioxygen activation and catalysis by redox enzymes, this work presents a Lewis acid improved dioxygen activation by an Fe^II(BPMEN)(OTf)₂ complex towards tryptophan 2,3-dioxygenase (TDO) activity for 3-methylindole and common olefinic CC bond oxygenation and cleavage (enzymatic Brønsted acid vs. chemical Lewis acid). It was found that the presence of a Lewis acid such as Sc³⁺ could substantially improve olefinic CC bond oxygenation and cleavage activity through Fe^II(BPMEN)(OTf)₂ catalyzed dioxygen activation. Notably, a more negative ρ value in the Hammett plot of para-substituted styrene oxygenations was observed in the presence of a stronger Lewis acid, disclosing the enhanced electrophilic oxygenation capability of the putative iron(III) superoxo species through its electrostatic interaction with a stronger Lewis acid. Thereof, this work has demonstrated a new strategy in catalyst design for dioxygen activation and catalysis for olefin oxygenation, a significant process in the chemical industry.

中文翻译：

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路易斯酸通过非血红素铁 (II) 复合物改善双氧活化，实现色氨酸 2,3-双加氧酶活性，实现烯烃氧化

环境温度附近的分子氧活化和催化是化学中长期存在的挑战。受氢键网络在双氧活化和氧化还原酶催化中的重要作用的启发，这项工作提出了路易斯酸通过 Fe ^II (BPMEN)(OTf) ₂复合物对色氨酸 2,3-双加氧酶 (TDO)改善双氧活化3-甲基吲哚和常见烯烃 CC键氧化和裂解的活性（酶促布朗斯台德酸与化学路易斯酸）。发现路易斯酸如 Sc ^{3+的存在可以通过 Fe II} (BPMEN)(OTf) ₂显着提高烯属 CC键氧化和裂解活性催化双氧活化。值得注意的是，在更强的路易斯酸存在下，观察到对位取代苯乙烯氧化的 Hammett 图中更负的ρ值，揭示了推定的铁（III）超氧物种通过与更强的静电相互作用增强的亲电氧化能力路易斯酸。因此，这项工作展示了一种新的催化剂设计策略，用于双氧活化和烯烃氧化催化，这是化学工业中的一个重要过程。