Electron spin resonance studies of kinetic effects of substituent and crown ether on intramolecular sodium cation exchange in 2,5-Di-Tert-amyl- and 2,5-Di-Tert-butyl-1,4-benzoquinone radical anions

Yoshimi Sueishi, Masamichi Kasahara, Kayo Okawa, Shunzo Yamamoto

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Upon an addition of crown ethers to a solution of 2,5-di-tert-amyl-1,4- benzoquinone (2,5-DAQ) and 2,5-di-tert-butyl-1,4-benzoquinone (2,5-DBQ) radical anions, the significant broadening of the two-center lines was observed in their electron spin resonance (ESR) spectra. The formation constants for the complexation of sodium cation with three kinds of crown ethers in 2,5-DAQ and 2,5-DBQ radical ion pairs were estimated, and the intramolecular two-site jumping rates of sodium cation complexed with crown ethers were determined. Differential effects of steric and crown ether were found in the intramolecular sodium cation migration. The stabilization of inclusion complex of sodium cation with crown ethers gives rise to the acceleration effects on the rates of intramolecular migration of cation/crown-ether complex. Based on the results, a kinetic explanation for the intramolecular sodium cation migration in the presence of crown ethers was given.

Original languageEnglish
Pages (from-to)1187-1196
Number of pages10
JournalZeitschrift fur Physikalische Chemie
Volume218
Issue number10
DOIs
Publication statusPublished - 2004

Fingerprint

Crown Ethers
quinones
Anions
Paramagnetic resonance
Cations
ethers
electron paramagnetic resonance
Sodium
sodium
anions
cations
Kinetics
kinetics
benzoquinone
Complexation
Stabilization
stabilization
inclusions
Ions

Keywords

  • Cation Migration
  • Crown Ether
  • Semiquinone Radical Anion
  • Substituent Effect

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Electron spin resonance studies of kinetic effects of substituent and crown ether on intramolecular sodium cation exchange in 2,5-Di-Tert-amyl- and 2,5-Di-Tert-butyl-1,4-benzoquinone radical anions",
abstract = "Upon an addition of crown ethers to a solution of 2,5-di-tert-amyl-1,4- benzoquinone (2,5-DAQ) and 2,5-di-tert-butyl-1,4-benzoquinone (2,5-DBQ) radical anions, the significant broadening of the two-center lines was observed in their electron spin resonance (ESR) spectra. The formation constants for the complexation of sodium cation with three kinds of crown ethers in 2,5-DAQ and 2,5-DBQ radical ion pairs were estimated, and the intramolecular two-site jumping rates of sodium cation complexed with crown ethers were determined. Differential effects of steric and crown ether were found in the intramolecular sodium cation migration. The stabilization of inclusion complex of sodium cation with crown ethers gives rise to the acceleration effects on the rates of intramolecular migration of cation/crown-ether complex. Based on the results, a kinetic explanation for the intramolecular sodium cation migration in the presence of crown ethers was given.",
keywords = "Cation Migration, Crown Ether, Semiquinone Radical Anion, Substituent Effect",
author = "Yoshimi Sueishi and Masamichi Kasahara and Kayo Okawa and Shunzo Yamamoto",
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language = "English",
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TY - JOUR

T1 - Electron spin resonance studies of kinetic effects of substituent and crown ether on intramolecular sodium cation exchange in 2,5-Di-Tert-amyl- and 2,5-Di-Tert-butyl-1,4-benzoquinone radical anions

AU - Sueishi, Yoshimi

AU - Kasahara, Masamichi

AU - Okawa, Kayo

AU - Yamamoto, Shunzo

PY - 2004

Y1 - 2004

N2 - Upon an addition of crown ethers to a solution of 2,5-di-tert-amyl-1,4- benzoquinone (2,5-DAQ) and 2,5-di-tert-butyl-1,4-benzoquinone (2,5-DBQ) radical anions, the significant broadening of the two-center lines was observed in their electron spin resonance (ESR) spectra. The formation constants for the complexation of sodium cation with three kinds of crown ethers in 2,5-DAQ and 2,5-DBQ radical ion pairs were estimated, and the intramolecular two-site jumping rates of sodium cation complexed with crown ethers were determined. Differential effects of steric and crown ether were found in the intramolecular sodium cation migration. The stabilization of inclusion complex of sodium cation with crown ethers gives rise to the acceleration effects on the rates of intramolecular migration of cation/crown-ether complex. Based on the results, a kinetic explanation for the intramolecular sodium cation migration in the presence of crown ethers was given.

AB - Upon an addition of crown ethers to a solution of 2,5-di-tert-amyl-1,4- benzoquinone (2,5-DAQ) and 2,5-di-tert-butyl-1,4-benzoquinone (2,5-DBQ) radical anions, the significant broadening of the two-center lines was observed in their electron spin resonance (ESR) spectra. The formation constants for the complexation of sodium cation with three kinds of crown ethers in 2,5-DAQ and 2,5-DBQ radical ion pairs were estimated, and the intramolecular two-site jumping rates of sodium cation complexed with crown ethers were determined. Differential effects of steric and crown ether were found in the intramolecular sodium cation migration. The stabilization of inclusion complex of sodium cation with crown ethers gives rise to the acceleration effects on the rates of intramolecular migration of cation/crown-ether complex. Based on the results, a kinetic explanation for the intramolecular sodium cation migration in the presence of crown ethers was given.

KW - Cation Migration

KW - Crown Ether

KW - Semiquinone Radical Anion

KW - Substituent Effect

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