The mechanism of inhibited oxidation of norbornene series bicycloolefins

Pliss, R. E.; Machtin, V. A.; Loshadkin, D. V.; Русаков, А. И.; Плисс, Е. М.

doi:10.1134/s0965544114050089

Cited by 4 publications

(4 citation statements)

References 6 publications

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“…Analogous results were obtained for the reactions of oxyperoxyl radicals. 5 The substantially higher rate constants (1•10 7 L mol -1 s -1 at the same temperature (323 K)) 20 are characteristic of the reactions of copper and manganese acetates with aminoperoxyl radicals of tertiary aliphatic amines. Note that for various peroxy radicals in nonaqueous media three orders of magnitude diff erence was found for the k 4 values, which decrease strongly on binding the metal into a complex.…”

Section: (Anamorphosis 2)mentioning

confidence: 99%

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Catalytic inhibition of olefin oxidation with Mn and Cu compounds

et al. 2021

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The rate constants and kinetic coeffi cients of inhibition (f kin ) for olefi ns oxidized with the transition metal compounds (M n ) were measured by highly sensitive microvolumometry at 323 K in combination with kinetic modeling. The cyclic mechanism of the reactions of hydr oxyl radicals with M n leading to the multiple chain termination was confi rmed as indicated by the observed eff ect of long-term inhibition of the oxidation of the substrates with M n and obtained values of f kin > 10 2 .

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Section: (Anamorphosis 2)mentioning

confidence: 99%

“…Values of k 4 for olefi n oxidation in the presence of CuCl 2 , CuAc 2 , and MnAc 2 ; 323 K Substrate k 4 •10 -5 /L mol -1 s -1 The estimation was performed by the kinetic modeling method using the Kinetika 2012 program19 similarly to the method described earlier 5. …”

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confidence: 99%

Catalytic inhibition of olefin oxidation with Mn and Cu compounds

et al. 2021

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“…Hydroperoxide radicals (

{HO}_{2}^{•}

) are carriers of liquid‐phase chain oxidation of organic molecules of different classes . During the oxidation of unsaturated compounds, depending on the substrate structure, the chain propagation takes place either via the addition reaction:

{HO}_{2}^{•}

+ >CC< (M)→ HOOM • (≡M • ) or via the hydrogen atom abstraction from the αCHbond:

{HO}_{2}^{•}

+ RH → HOOH + R • , or these routes are parallel . Along with liquid‐phase reactions, the possibility of

{HO}_{2}^{•}

formation is also considered in micro‐heterogeneous systems, particularly, the oxidation of methyl linoleate in micelles .…”

Section: Introductionmentioning

confidence: 99%

“…It is assumed that the transition state of peroxy radicals addition reactions (in particular,

{HO}_{2}^{•}

) to double bonds is a charge‐transfer complex (Scheme ), which allows using the Kirkwood–Onsager equation to evaluate the role of nonspecific solvation :

\begin{matrix} true \\ right prefixlg k = prefixlg k^{0} - \frac{1}{2, 3 k_{B} T} \frac{ε - 1}{2 ε + 1} ((), \frac{μ_{1}^{2}}{r_{1}^{3}} + \frac{μ_{2}^{2}}{r_{2}^{3}} - \frac{μ_{\neq}^{2}}{r_{\neq}^{3}}) \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

The Role of Solvation in the Kinetics and the Mechanism of Hydroperoxide Radicals Addition to π‐Bonds of 1,2‐Diphenylethylene and 1,4‐Diphenylbutadiene‐1,3

Плисс

Machtin

Soloviev

et al. 2018

Int J of Chemical Kinetics

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A combination of microcalorimetry, the rotating sector method, and ESR at 323 K in the environment of 10 solvents of different polarities was used to measure rate constants of addition of hydroperoxide radicals (HO • 2 ) to π bonds of trans-1,2-diphenylethylene and trans,trans-1,4-diphenylbutadiene-1,3 (k 2 ) and disproportionation rate constants of these radicals (k 3 ). With increasing dielectric constant of the medium, k 2 values increase from 69 to 410 M −1 · s −1 , and k 3 values almost do not change and are in the range of (1.0 ± 0.2) × 10 8 M −1 · s −1 . A linear dependence of logarithm values of rate constants from the dielectric constant of the medium in the coordinates of the Kirkwood-Onsager equation was found that allows to make a conclusion about the effect of nonspecific solvation in the studied systems. The quantum-chemical analysis (NWChem, DFT B3LYP/6-311G**) of the detailed mechanism for HO • 2 addition shows that the influence of the medium polarity reflects the superposition of the effects of nonspecific and specific solvation. The scale of the polar effect will depend on how different solvation energies of the transition and the initial reaction complexes. If a value of the solvation energy of the transition complex is larger than the solvation energy of the initial reaction complex, then the reaction rate should increase with an increase of the solvent's polarity and decrease otherwise. C

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