Hydroxylation of Unactivated C(sp3)-H Bonds with m-Chloroperbenzoic Acid Catalyzed by an Iron(III) Complex Supported by a Trianionic Planar Tetradentate Ligand

被引：14

作者：

Morimoto, Yuma ^{[2
]}

Hanada, Shinichi ^{[1
]}

Kamada, Ryusuke ^{[2
]}

Fukatsu, Arisa ^{[1
]}

Sugimoto, Hideki ^{[2
]}

Itoh, Shinobu ^{[2
]}

机构：

[1] Osaka Univ, Grad Sch Engn, Dept Mat & Life Sci, Div Adv Sci & Biotechnol, Suita, Osaka 5650871, Japan

[2] Osaka Univ, Grad Sch Engn, Dept Mol Chem, Div Appl Chem, Suita, Osaka 5650871, Japan

来源：

INORGANIC CHEMISTRY | 2021年 / 60卷 / 11期

关键词：

C-H BONDS; ALKANE-HYDROXYLATION; OXOIRON(IV) COMPLEX; BETA-DIKETIMINATE; REACTIVITY; OXIDATION; EPR; HYDROCARBONS; MECHANISM; RADICALS;

D O I：

10.1021/acs.inorgchem.0c03469

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Hydroxylation of cyclohexane with m-chloroperbenzoic acid was examined in the presence of an iron(III) complex supported by a trianionic planar tetradentate ligand. The present reaction system shows a high turnover number of 2750 with a high product selectivity of alcohol (93%). The turnover frequency was 0.51 s(-1), and the second-order rate constant (k) for the C-H bond activation of cyclohexane was 1.08 M-1 s(-1), which is one of the highest values among the iron complexes in the oxidation of cyclohexane so far reported. The present catalytic system can be adapted to the hydroxylation of substrates having only primary C-H bonds such as 2,2,3,3-tetramethylbutane as well as gaseous alkanes such as butane, propane, and ethane. The involvement of an iron(III) acyl peroxido complex as the reactive species was suggested by spectroscopic measurements of the reaction solution.

引用

页码：7641 / 7649

页数：9

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