Theoretical study of the relative reactivity of chloroethenes with atmospheric oxidants (OH, NO3, O(3P), Cl(2P) and Br(2P))

Literature Information

Publication Date 2002-02-14
DOI 10.1039/B108856B
Impact Factor 3.676
Authors

María T. Baumgartner, Raúl A. Taccone, Mariano A. Teruel, Silvia I. Lane


View Original

Abstract

The reactivity of a series of chloroethenes with different electrophiles of tropospheric and stratospheric interest is analyzed by frontier molecular orbital theory and a correlation with calculated orbital energies is investigated. The reactions of CH2CHCl; CH2CCl2; (Z)-CHClCHCl; (E)-CHClCHCl; CHClCCl2 and CCl2CCl2 with O(3P), Cl(2P), Br(2P) atoms and with OH and NO3 radicals were studied using semiempirical methods (AM1 and PM3) and ab initio calculations at the HF and B3LYP levels of theory with the 6-31G** basis set, using the Gaussian 98 suite of programs. In contrast to the majority of reaction series of small radicals and molecules with alkenes and alkanes, the rate constants for the reactions with halogenated ethenes do not correlate with the ionization potential of the halogenated ethene. The energy and the carbon–carbon π-bonding form of the HOMO change on addition of chlorine atoms as substituents to the carbon–carbon σ-bonding framework of the alkenes. For the reactions studied the complete interaction HOMO–SOMO was considered, taking into account the contribution of the different atomic orbitals to the HOMO of the chloroethene through the atomic orbital coefficients, and a good correlation with the experimental values was obtained.

Related Literature

Inside front cover

Cover

DOI: 10.1039/D0OB90054K

A base-promoted tandem approach to bicyclic 8-membered ring ketones

Emerson E. F. dos Santos, Gabriela F. P. de Souza, Deborah A. Simoni, Airton G. Salles, Jr

2020-04-13 Communication

DOI: 10.1039/D0OB00618A

Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?

Kolle E. Thomas, Christine M. Beavers, Abhik Ghosh

2020-03-26 Paper

DOI: 10.1039/D0OB00452A

Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes

Mingyang Yang, Zhimin Xing, Bowen Fang, Xingang Xie, Xuegong She

2019-12-06 Paper

DOI: 10.1039/C9OB02517K

The effect of spermidine on guanine decomposition via photoinduced electron transfer in DNA

Mayu Esumi, Shunsuke Sakurai, Makiko Tanaka

2019-11-27 Communication

DOI: 10.1039/C9OB01860C

Branched lipid chains to prepare cationic amphiphiles producing hexagonal aggregates: supramolecular behavior and application to gene delivery

Amal Bouraoui, Rosy Ghanem, Mathieu Berchel, Laure Deschamps, Véronique Vié, Gilles Paboeuf, Tony Le Gall, Tristan Montier, Paul-Alain Jaffrès

2019-12-04 Paper

DOI: 10.1039/C9OB02381J

The endo-aza-Michael addition in the synthesis of piperidines and pyrrolidines

Roderick W. Bates, Weiting Ko, Viktor Barát

2020-01-16 Review Article

DOI: 10.1039/C9OB02388G

Rhodium(iii)-catalyzed ortho-C–H amidation of 2-arylindazoles with a dioxazolone as an amidating reagent

Payel Ghosh, Sadhanendu Samanta, Alakananda Hajra

2020-01-27 Communication

DOI: 10.1039/C9OB02756D

Contents list

Front/Back Matter

DOI: 10.1039/D0OB90037K

Recent advances in cobalt-catalysed C–H functionalizations

Alessio Baccalini, Stefania Vergura, Pravas Dolui, Giuseppe Zanoni, Debabrata Maiti

2019-11-07 Review Article

DOI: 10.1039/C9OB01994D

You might also like

Compound Q&A

What regulatory guidelines apply to 6-Bromo-2-methylimidazo[1,2-a]pyrimidine (CAS: 1111638-05-1)?

6-Bromo-2-methylimidazo[1,2-a]pyrimidine (CAS: 1111638-05-1) falls under various...

1111638-05-16-Bromo-2-methylimid...
Compound Q&A

Are there alternatives to 1-Pyrrolidineethanol, β-methyl-α-phenyl-, (αS,βR) (CAS: 123620-80-4) in synthesis?

While there are no direct alternatives, similar compounds like 1-Pyrrolidineetha...

123620-80-41-Pyrrolidineethanol...
Compound Q&A

Is 4-Methyl-2,6-bis(2-methyl-2-propanyl)phenyl methylcarbamate (CAS: 1918-11-2) safe?

4-Methyl-2,6-bis(2-methyl-2-propanyl)phenyl methylcarbamate (CAS: 1918-11-2) is ...

1918-11-24-Methyl-2,6-bis(2-m...
Compound Q&A

How should 2-(3-Bromo-4-fluorophenyl)-1,3-dioxolane (CAS: 77771-04-1) be stored?

2-(3-Bromo-4-fluorophenyl)-1,3-dioxolane (CAS: 77771-04-1) should be stored in a...

77771-04-12-(3-Bromo-4-fluorop...
Compound Q&A

What are the physical and chemical properties of 4,5,6,7-Tetrahydro-1H-indazole hydrochloride (CAS: 18161-11-0)?

4,5,6,7-Tetrahydro-1H-indazole hydrochloride is a white crystalline solid with a...

18161-11-04,5,6,7-Tetrahydro-1...
Compound Q&A

What is (2R)-1-Methoxy-3-phenyl-2-propanamine (CAS: 59919-07-2)?

(2R)-1-Methoxy-3-phenyl-2-propanamine is a chiral organic compound with the CAS ...

59919-07-2(2R)-1-Methoxy-3-phe...
Compound Q&A

What industries use Ethyl 1-(1-phenylethyl)-1H-imidazole-5-carboxylate (CAS: 56649-47-9)?

Ethyl 1-(1-phenylethyl)-1H-imidazole-5-carboxylate is used in various industries...

56649-47-9Ethyl 1-(1-phenyleth...
Compound Q&A

What regulatory guidelines apply to 4-[(1E,3S)-1-(4-Hydroxyphenyl)-1,4-pentadien-3-yl]phenol (CAS: 17676-24-3)?

4-[(1E,3S)-1-(4-Hydroxyphenyl)-1,4-pentadien-3-yl]phenol (CAS: 17676-24-3) falls...

17676-24-34-[(1E,3S)-1-(4-Hydr...
Compound Q&A

What industries use (S)-3-Amino-5-phenylpentanoic acid hydrochloride (CAS: 331846-97-0)?

(S)-3-Amino-5-phenylpentanoic acid hydrochloride is primarily used in the pharma...

331846-97-0(S)-3-Amino-5-phenyl...
Compound Q&A

How is 7-methoxy-1-benzothiophene-2-carboxylic acid (CAS: 88791-07-5) typically synthesized?

7-Methoxy-1-benzothiophene-2-carboxylic acid is typically synthesized by reactin...

88791-07-57-methoxy-1-benzothi...

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.