Competition between electron transfer and base-induced elimination mechanisms in the gas-phase reactions of superoxide with alkyl hydroperoxides

Literature Information

Publication Date 2021-02-16
DOI 10.1039/D0CP05761D
Impact Factor 3.676
Authors

Ezequiel Fragoso Vieira Leitão, Miguel Angelo Fonseca de Souza, Silmar Andrade do Monte, Elizete Ventura


View Original

Abstract

Understanding the mechanism responsible for peroxides decomposition is essential to explain several biochemical processes. The mechanisms of the intrinsic reactions between the superoxide radical anion (O2˙−) and methyl, ethyl, and tert-butyl hydroperoxides (ROOH, with R = Me, Et, and t-Bu) have been characterized to understand the mechanism responsible for peroxides decomposition. The reaction energy diagrams suggest a competition between the spin-allowed and spin-forbidden electron transfer (ET), and base-induced elimination (ECO2) mechanisms. In all cases, the spin-allowed ET mechanism describes formation of the ozonide anion radical (O3˙−), either complexed with an alcohol molecule or separated. For the O2˙−/MeOOH(EtOOH) reactions, HCO2− (MeCO2−) + H2O + HO˙ and OH− + CH2O(MeCHO) + HO2˙ products are associated with the spin-forbidden ET and ECO2 channels, respectively. On the other hand, for the reaction between O2˙− and t-BuOOH, the spin-forbidden ET route describes formation of the MeCOCH2− enolate (either separated or hydrated) along with the methyl peroxyl (MeO2˙) radical. In addition, the regeneration of O2˙−via spin-forbidden ET and ECO2 channels was also characterized from the decomposition of ROOH, yielding diols (CH2(OH)2 and MeCH(OH)2), aldehydes (CH2O and MeCHO), and oxirane (cyc-CH2CMe2O).

Related Literature

Inside-outside self-assembly of light-activated fast-release liposomes

Natalie Forbes, Jeong Eun Shin, Maria Ogunyankin, Joseph A. Zasadzinski

2015-02-23 Paper

DOI: 10.1039/C4CP05881J

Non-fullerene acceptors: exciton dissociation with PTCDA versus C60

Gregory J. Dutton, Steven W. Robey

2015-05-22 Paper

DOI: 10.1039/C5CP02800K

Like-charge ion pairs of hydronium and hydroxide in aqueous solution?

Manik Kumer Ghosh, Tae Hoon Choi, Cheol Ho Choi

2015-05-26 Communication

DOI: 10.1039/C5CP02182K

Thermostructural behaviour of Ni–Cr materials: modelling of bulk and nanoparticle systems

Jose M. Ortiz-Roldan, A. Rabdel Ruiz-Salvador, Sofía Calero, Francisco Montero-Chacón, Elena García-Pérez, Javier Segurado, Ignacio Martin-Bragado, Said Hamad

2015-05-07 Paper

DOI: 10.1039/C5CP01785H

Rayleigh light scattering properties of atmospheric molecular clusters consisting of sulfuric acid and bases

Jonas Elm, Patrick Norman, Kurt V. Mikkelsen

2015-03-18 Paper

DOI: 10.1039/C5CP01012H

Biophysics of α-synuclein induced membrane remodelling

Zheng Shi, Jonathan N. Sachs, Elizabeth Rhoades, Tobias Baumgart

2015-02-02 Paper

DOI: 10.1039/C4CP05883F

Contents list

Front/Back Matter

DOI: 10.1039/C5CP90099A

You might also like

Compound Q&A

What are the main uses of (3alpha,5alpha)-3-Hydroxypregnane-11,20-dione (CAS: 23930-19-0)?

(3alpha,5alpha)-3-Hydroxypregnane-11,20-dione is primarily used in the pharmaceu...

23930-19-0(3alpha,5alpha)-3-Hy...
Compound Q&A

What is the market or research trend for 4-Amino-6-chloro-2-pyridinecarboxylic acid (CAS: 546141-56-4)?

The market for 4-Amino-6-chloro-2-pyridinecarboxylic acid (CAS: 546141-56-4) is ...

546141-56-44-Amino-6-chloro-2-p...
Compound Q&A

Are there alternatives to (2-Benzoylethyl)trimethylammonium chloride (CAS: 24472-88-6) in synthesis?

Alternatives to (2-Benzoylethyl)trimethylammonium chloride (CAS: 24472-88-6) in ...

24472-88-6(2-Benzoylethyl)trim...
Compound Q&A

Is N-[4-Nitro-3-(trifluoromethyl)phenyl]acetamide (CAS: 393-12-4) safe?

N-[4-Nitro-3-(trifluoromethyl)phenyl]acetamide (CAS: 393-12-4) is generally safe...

393-12-4N-[4-Nitro-3-(triflu...
Compound Q&A

Are there alternatives to N,N'-Bis(3-aminopropyl)-1,3-propanediamine (CAS: 4605-14-5) in synthesis?

There are alternatives to N,N'-Bis(3-aminopropyl)-1,3-propanediamine (CAS: 4605-...

4605-14-5N,N'-Bis(3-aminoprop...
Compound Q&A

What precautions should be taken when handling Aluminium trihexadecanoate (CAS: 555-35-1)?

When handling Aluminium trihexadecanoate, it is important to use appropriate per...

555-35-1Aluminium trihexadec...
Compound Q&A

What is (1,1-Dioxido-3-oxo-1,2-benzothiazol-2(3H)-yl)acetic acid (CAS: 52188-11-1)?

(1,1-Dioxido-3-oxo-1,2-benzothiazol-2(3H)-yl)acetic acid is a chemical compound ...

52188-11-1(1,1-Dioxido-3-oxo-1...
Compound Q&A

Are there alternatives to 5,5-dimethyloxolan-2-one (CAS: 3123-97-5) in synthesis?

Several alternatives to 5,5-dimethyloxolan-2-one (CAS: 3123-97-5) can be used in...

3123-97-55,5-dimethyloxolan-2...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.