Reactions of cation radicals of EE systems. 9. Kinetics and mechanism of the reaction of thianthrene cation radical with nitrate ion

Jeanne E Pemberton, Gregory L. McIntire, Henry N. Blount, John F. Evans

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The stoichiometry and dynamics of the reaction of thianthrene cation radical with nitrate ion have been studied in acetonitrile, butyronitrile, nitromethane, nitrobenzene, and methylene chloride. In all cases, the reaction is found to yield thianthrene 5-oxide exclusively, with no detectable thianthrene being regenerated during the reaction. The observed rate law in all solvents studied was found to be second order in thianthrene cation radical and first order in nitrate ion. The mechanism proposed for this reaction is analogous to the half-regeneration pathway but differs in that a bridged intermediate comprised of two cation radicals and a nitrate ion decomposes to form two molecules of the oxide and NO+. The observed rate constants, corrected for association equilibria involving nitrate ion, exhibit a linear inverse dependence on Dimroth-Reichardt solvent polarity (ET) parameters, thereby suggesting formation of the bridged intermediate as the rate-determining step in the reaction.

Original languageEnglish (US)
Pages (from-to)2696-2703
Number of pages8
JournalJournal of Physical Chemistry
Volume83
Issue number21
StatePublished - 1979
Externally publishedYes

Fingerprint

Nitrates
Cations
nitrates
Positive ions
Ions
cations
Kinetics
kinetics
ions
Oxides
Nitrobenzene
Methylene Chloride
Dichloromethane
Acetonitrile
nitromethane
Stoichiometry
oxides
nitrobenzenes
Rate constants
regeneration

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Reactions of cation radicals of EE systems. 9. Kinetics and mechanism of the reaction of thianthrene cation radical with nitrate ion. / Pemberton, Jeanne E; McIntire, Gregory L.; Blount, Henry N.; Evans, John F.

In: Journal of Physical Chemistry, Vol. 83, No. 21, 1979, p. 2696-2703.

Research output: Contribution to journalArticle

@article{af610b6e40c24c4795e08d2852048521,
title = "Reactions of cation radicals of EE systems. 9. Kinetics and mechanism of the reaction of thianthrene cation radical with nitrate ion",
abstract = "The stoichiometry and dynamics of the reaction of thianthrene cation radical with nitrate ion have been studied in acetonitrile, butyronitrile, nitromethane, nitrobenzene, and methylene chloride. In all cases, the reaction is found to yield thianthrene 5-oxide exclusively, with no detectable thianthrene being regenerated during the reaction. The observed rate law in all solvents studied was found to be second order in thianthrene cation radical and first order in nitrate ion. The mechanism proposed for this reaction is analogous to the half-regeneration pathway but differs in that a bridged intermediate comprised of two cation radicals and a nitrate ion decomposes to form two molecules of the oxide and NO+. The observed rate constants, corrected for association equilibria involving nitrate ion, exhibit a linear inverse dependence on Dimroth-Reichardt solvent polarity (ET) parameters, thereby suggesting formation of the bridged intermediate as the rate-determining step in the reaction.",
author = "Pemberton, {Jeanne E} and McIntire, {Gregory L.} and Blount, {Henry N.} and Evans, {John F.}",
year = "1979",
language = "English (US)",
volume = "83",
pages = "2696--2703",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Reactions of cation radicals of EE systems. 9. Kinetics and mechanism of the reaction of thianthrene cation radical with nitrate ion

AU - Pemberton, Jeanne E

AU - McIntire, Gregory L.

AU - Blount, Henry N.

AU - Evans, John F.

PY - 1979

Y1 - 1979

N2 - The stoichiometry and dynamics of the reaction of thianthrene cation radical with nitrate ion have been studied in acetonitrile, butyronitrile, nitromethane, nitrobenzene, and methylene chloride. In all cases, the reaction is found to yield thianthrene 5-oxide exclusively, with no detectable thianthrene being regenerated during the reaction. The observed rate law in all solvents studied was found to be second order in thianthrene cation radical and first order in nitrate ion. The mechanism proposed for this reaction is analogous to the half-regeneration pathway but differs in that a bridged intermediate comprised of two cation radicals and a nitrate ion decomposes to form two molecules of the oxide and NO+. The observed rate constants, corrected for association equilibria involving nitrate ion, exhibit a linear inverse dependence on Dimroth-Reichardt solvent polarity (ET) parameters, thereby suggesting formation of the bridged intermediate as the rate-determining step in the reaction.

AB - The stoichiometry and dynamics of the reaction of thianthrene cation radical with nitrate ion have been studied in acetonitrile, butyronitrile, nitromethane, nitrobenzene, and methylene chloride. In all cases, the reaction is found to yield thianthrene 5-oxide exclusively, with no detectable thianthrene being regenerated during the reaction. The observed rate law in all solvents studied was found to be second order in thianthrene cation radical and first order in nitrate ion. The mechanism proposed for this reaction is analogous to the half-regeneration pathway but differs in that a bridged intermediate comprised of two cation radicals and a nitrate ion decomposes to form two molecules of the oxide and NO+. The observed rate constants, corrected for association equilibria involving nitrate ion, exhibit a linear inverse dependence on Dimroth-Reichardt solvent polarity (ET) parameters, thereby suggesting formation of the bridged intermediate as the rate-determining step in the reaction.

UR - http://www.scopus.com/inward/record.url?scp=33845560790&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845560790&partnerID=8YFLogxK

M3 - Article

VL - 83

SP - 2696

EP - 2703

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 21

ER -