Alkane‐Oxidizing Systems Based on Metal Complexes. Radical Versus Nonradical Mechanisms<sup>1</sup>

Shul’pin, Georgiy B.

doi:10.1002/9781119379256.ch3

Cited by 13 publications

(7 citation statements)

References 76 publications

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“…Complexes of transition metals are known to catalyze the oxidation of hydrocarbons and alcohols with peroxides [46][47][48][49][50]. In the present work, we found that complex 1 exhibited catalytic activity in the oxidation of cyclohexane and other alkanes with H 2 O 2 in acetonitrile, in the presence of nitric acid.…”

Section: Oxidation Of Hydrocarbons and Alcohols With Peroxidessupporting

confidence: 59%

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

et al. 2019

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The self-assembly synthesis of copper-sodium phenylsilsesquioxane in the presence of 1,1-bis(diphenylphosphino)methane (dppm) results in an unprecedented cage-like product: [(PhSiO 1,5 ) 6 ] 2 [CuO] 4 [NaO 0.5 ] 4 [dppmO 2 ] 2 1. The most intriguing feature of the complex 1 is the presence of two oxidized dppm species that act as additional O-ligands for sodium ions. Two cyclic phenylsiloxanolate (PhSiO 1,5 ) 6 ligands coordinate in a sandwich manner with the copper(II)-containing layer of the cage. The structure of 1 was established by X-ray diffraction analysis. Complex 1 was shown to be a very good catalyst in the oxidation of alkanes and alcohols with hydrogen peroxide or tert-butyl hydroperoxide in acetonitrile solution. Thus, cyclohexane (CyH), was transformed into cyclohexyl hydroperoxide (CyOOH), which could be easily reduced by PPh 3 to afford stable cyclohexanol with a yield of 26% (turnover number (TON) = 240) based on the starting cyclohexane. 1-Phenylethanol was oxidized by tert-butyl hydroperoxide to give acetophenone in an almost quantitative yield. The selectivity parameters of the oxidation of normal and branched alkanes led to the conclusion that the peroxides H 2 O 2 and tert-BuOOH, under the action of compound (1), decompose to generate the radicals HO • and tert-BuO • which attack the C-H bonds of the substrate.

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Section: Oxidation Of Hydrocarbons and Alcohols With Peroxidessupporting

confidence: 59%

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

et al. 2019

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“…The follo ivity parameters were obtained for the oxidation of n-heptane: C(1):C(2):C(3):C( :7.2:7.9. These data as well as the character of dependence of the initial cyclohexane oxid n the initial hydrocarbon concentration (approaching a plateau at [cyclohexane]0 > 0. te that the reaction occurs with the participation of hydroxyl radicals and alkyl hydropero formed as the main primary products (Figure 4) [46][47][48]. The oxygenation -dimethylcyclohexane with H2O2 catalyzed by complex 1 gave corresponding isomeric ter ols in a trans/cis ratio of 0.8.…”

Section: Introductionmentioning

confidence: 99%

Cu42Ge24Na4—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity

et al. 2018

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Unprecedented germanium-based sesquioxane exhibits an extremely high nuclearity (Cu42Ge24Na4) and unusual encapsulation features. The compound demonstrated a high catalytic activity in the oxidative amidation of alcohols, with cost-effective catalyst loading down to 400 ppm of copper, and in the oxidation of cyclohexane and other alkanes with H2O2 in acetonitrile in the presence of nitric acid. Selectivity parameters and the mode of dependence of initial cyclohexane oxidation rate on initial concentration of the hydrocarbon indicate that the reaction occurs with the participation of hydroxyl radicals and alkyl hydroperoxides are formed as the main primary product. Alcohols have been transformed into the corresponding ketones by the catalytic oxidation with tert-butyl hydroperoxide.

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“…Transition metal complexes bearing voluminous organic ligands are widely used as catalysts in various organic reactions including CH-functionalization (see reviews and original works [77][78][79][80][81][82][83][84][85]): "Over the past 50 years organic chemists have invented an incredible number of synthetically useful transition metal catalyzed reaction types. In the most cases, the transition metals are complexed to sterically and electronically tunable organic ligands, which govern activity and selectivity" [80].…”

Section: Catalytic Oxidations Of Alkanes and Alcoholsmentioning

confidence: 99%

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

et al. 2019

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Self-assembly of copper(II)phenylsilsesquioxane assisted by the use of 1,10-phenanthroline (phen) results in isolation of two unusual cage-like compounds: (PhSiO1,5)12(CuO)4(NaO0.5)4(phen)4 1 and (PhSiO1,5)6(PhSiO1,5)7(HO0.5)2(CuO)5(O0.25)2(phen)3 2. X-Ray diffraction study revealed extraordinaire molecular architectures of both products. Namely, complex 1 includes single cyclic (PhSiO1,5)12 silsesquioxane ligand. Four sodium ions of 1 are additionally ligated by 1,10-phenanthrolines. In turn, “sodium-less” complex 2 represents coordination of 1,10-phenanthrolines to copper ions. Two silsesquioxane ligands of 2 are: (i) noncondensed cubane of a rare Si6-type and (ii) unprecedented Si7-based ligand including two HOSiO1.5 fragments. These silanol units were formed due to removal of phenyl groups from silicon atoms, observed in mild conditions. The presence of phenanthroline ligands in products 1 and 2 favored the π–π stacking interactions between neighboring cages. Noticeable that in the case of 1 all four phenanthrolines participated in such supramolecular organization, unlike to complex 2 where one of the three phenanthrolines is not “supramolecularly active”. Complexes 1 and 2 were found to be very efficient precatalysts in oxidations with hydroperoxides. A new method for the determination of the participation of hydroxyl radicals has been developed.

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Alkane‐Oxidizing Systems Based on Metal Complexes. Radical Versus Nonradical Mechanisms¹

Cited by 13 publications

References 76 publications

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

Cu42Ge24Na4—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

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Alkane‐Oxidizing Systems Based on Metal Complexes. Radical Versus Nonradical Mechanisms1

Cited by 13 publications

References 76 publications

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

Cu42Ge24Na4—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

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Alkane‐Oxidizing Systems Based on Metal Complexes. Radical Versus Nonradical Mechanisms¹