Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family,ChemCatChem

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Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family
ChemCatChem ( IF 3.8 ) Pub Date : 2018-07-20 , DOI: 10.1002/cctc.201800832
Nikolay V. Tkachenko _{1,

2} , Roman V. Ottenbacher _{1,

2} , Oleg Y. Lyakin _{1,

2} , Alexandra M. Zima _{1,

2} , Denis G. Samsonenko _{2,

3} , Evgenii P. Talsi _{1,

2} , Konstantin P. Bryliakov _{1,

2}

Affiliation

The catalytic activity of a series of iron complexes of the PDP family (PDP=N,N′‐bis(2‐pyridylmethyl)‐2,2′‐bipyrrolidine) in the oxidation of aromatic substrates with H₂O₂ has been studied. In the presence of acetic acid, these complexes efficiently catalyze the oxidation of benzene and alkylbenzenes with high selectivity for oxygen incorporation into the aromatic ring (up to 93 %), performing up to 84 catalytic turnovers. The parent complex, [(PDP)(OTf)₂], has demonstrated the highest catalytic efficiency and aromatic oxidation selectivity. The yield of products of oxidation of different substrates increases in line with increasing number of electron‐donating alkyl groups of the substrates: halogenbenzenes<benzene<monoalkylbenzenes<dialkylbenzenes, which, together with the results of competitive oxidation experiments and the observation of inverse primary k_H/k_D (0.90–0.92), agrees with the S_EAr oxidation mechanism. Low‐temperature EPR studies have witnessed the presence of low‐spin (g₁=2.071, g₂=2.008, g₃=1.960) perferryl intermediates, demonstrating direct reactivity toward benzene. The oxidation of m‐xylene in the presence of H₂¹⁸O has shown the same probability of ¹⁸O incorporation into the aromatic ring and the aliphatic moieties, which is indicative that both the aromatic and aliphatic oxidations are conducted by the same active species.

中文翻译：

在PDP族铁络合物存在下用H2O2进行高效CH-H芳香氧化

研究了PDP家族的一系列铁配合物（PDP = N，N'-双（2-吡啶基甲基）-2,2'-联吡咯烷）在H ₂ O ₂氧化芳族底物上的催化活性。在乙酸的存在下，这些络合物有效地催化苯和烷基苯的氧化，并且具有高选择性地将氧掺入芳环中（高达93％），执行多达84次催化转化。父复合体[[PDP] [OTf）₂，已显示出最高的催化效率和芳族氧化选择性。不同底物的氧化产物的产率随底物的供电子烷基数目的增加而增加：卤素苯<苯<单烷基苯<二烷基苯，其与竞争性氧化实验的结果和反伯k的观察一起观察_ħ / ķ _d（0.90-0.92），同意在S _Ë氩氧化机理。低温EPR研究表明存在低旋转（g ₁ = 2.071，g ₂ = 2.008，g ₃= 1.960）perferryl中间体，表明对苯具有直接反应性。的氧化米二甲苯在H存在₂¹⁸ O具有示出的相同的概率¹⁸ ö并入芳香环和脂族结构部分，其表示的是，芳香族和脂肪族氧化由相同的活性种进行。

更新日期：2018-07-20

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