A Mononuclear Non-heme Iron(III)–Peroxo Complex with an Unprecedented High O–O Stretch and Electrophilic Reactivity
A Mononuclear Non-heme Iron(III)–Peroxo Complex with an Unprecedented High O–O Stretch and Electrophilic Reactivity
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具有前所未有的高 O-O 拉伸和亲电反应性的单核非血红素铁 (III)-过氧复合物
DOI：
10.1021/jacs.1c03358
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发表时间：
2021
影响因子：
15
通讯作者：
Sarangi, Ritimukta
中科院分区：
文献类型：
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作者：
Zhu, Wenjuan;Jang, Semin;Xiong, Jin;Ezhov, Roman;Li, Xiao-Xi;Kim, Taeyeon;Seo, Mi Sook;Lee, Yong-Min;Pushkar, Yulia;Sarangi, Ritimukta
合成了一种单核非血红素铁(III) -过氧配合物[Fe(III)(O2)(13-TMC)]+(1)，并对其进行了光谱表征；电子顺磁共振、Mössbauer、x射线吸收、共振拉曼光谱和质谱表征支持高自旋=5/2Fe（III）结合o2单元。一个值得注意的观察结果是过氧配体的异常高νO-Oat ~ 1000 cm - 1。在反应性方面，1在H原子抽离（HAA）和O原子转移（OAT）反应中表现出亲电性。在HAT反应中，9,10-二氢蒽氧化的动力学同位素效应（KIE）值为5.8。在OAT反应中，p- x取代硫代苯甲醚的氧化在Hammett图中确定了负的ρ值为- 0.61。另一个有趣的观察结果是苯甲醛衍生物氧化过程中1的亲电反应性，如Hammett图中的负ρ值为- 0.77，KIE值为2.2。据我们所知，本研究报告了单核非血红素铁(III) -过氧配合物的第一个例子，该配合物在氧化反应中具有异常高的ν o - o值和前所未有的亲电反应性。
A mononuclear non-heme iron(III)–peroxo complex, [Fe(III)(O2)(13-TMC)]+(1), was synthesized and characterized spectroscopically; the characterization with electron paramagnetic resonance, Mössbauer, X-ray absorption, and resonance Raman spectroscopies and mass spectrometry supported a high-spinS=5/2Fe(III) species binding an O2unit. A notable observation was an unusually high νO–Oat ∼1000 cm–1for the peroxo ligand. With regard to reactivity,1showed electrophilic reactivity in H atom abstraction (HAA) and O atom transfer (OAT) reactions. In the HAT reaction, a kinetic isotope effect (KIE) value of 5.8 was obtained in the oxidation of 9,10-dihydroanthracene. In the OAT reaction, a negative ρ value of −0.61 in the Hammett plot was determined in the oxidation ofp-X-substituted thioanisoles. Another interesting observation was the electrophilic reactivity of1in the oxidation of benzaldehyde derivatives, such as a negative ρ value of −0.77 in the Hammett plot and a KIE value of 2.2. To the best of our knowledge, the present study reports the first example of a mononuclear non-heme iron(III)–peroxo complex with an unusually high νO–Ovalue and unprecedented electrophilic reactivity in oxidation reactions.