EPR and DFT Study of Copper(II) Complex with 1,10-Phenanthroline as Catalyst for Oxidation of Cyclohexanol with tert-Butyl Hydroperoxide

Кокорин, А. И.; Голубева, Е. Н.; Vinogradov, Mikhail M.; Kozlov, Yu. N.; Shul’pin, Georgiy B.

doi:10.1007/s00723-022-01467-x

Cited by 2 publications

(2 citation statements)

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“…We discovered that complex 3 exhibits high catalytic activity in the oxidation of saturated hydrocarbons. The data obtained in the oxidation of cyclohexane with hydrogen peroxide for complex 3 showed that in the presence of HNO 3 , the reactions proceed much faster, which is consistent with our previous studies of oxidative processes using copper complexes as catalysts [ 68 , 69 , 70 , 86 , 88 , 89 , 90 , 91 ]. Nitric acid is a co-catalyst in these reactions.…”

Section: Resultssupporting

confidence: 90%

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Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity

Bilyachenko

Khrustalev²,

Gutsul³

et al. 2022

Molecules

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A series of phenylsilsesquioxane-benzoate heptacopper complexes 1–3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2–3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.

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Section: Resultssupporting

confidence: 90%

“…Copper complexes have systematically demonstrated high activity in these oxidation processes [ 80 , 81 , 82 , 83 , 84 , 85 ]. Recently, we also have found several copper complexes exhibited high efficiency in the oxidation of organic compounds with peroxides [ 86 , 87 , 88 , 89 , 90 , 91 , 92 ].…”

Section: Resultsmentioning

confidence: 99%