Intramolecular assistance of electron transfer from heteroatom compounds. Electrochemical oxidation of 2-(2-pyridyl)ethyl-substituted ethers, sulfides, and selenides

Mitsuru Watanabe, Seiji Suga, Jun Ichi Yoshida

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8 Citations (Scopus)

Abstract

Organoheteroatom compounds having a 2-(2-pyridyl)ethyl group were synthesized and their oxidation potentials were determined by rotating disk electrode voltammetry. The oxidation potentials were found to be less positive than those of the corresponding compounds having a phenyl group in place of the pyridyl group. The dynamic coordination of the pyridyl group to the heteroatom, which stabilizes the cation radical intermediate, seems to be responsible for facilitating the electron transfer. The magnitude of the intramolecular assistance increases along with an increase in the oxidation potential of the parent compounds. This tendency can be explained in terms of the energy match between the nonbonding p orbital of the pyridyl nitrogen and the HOMO of the parent heteroatom compound.

Original languageEnglish
Pages (from-to)243-247
Number of pages5
JournalBulletin of the Chemical Society of Japan
Volume73
Issue number1
DOIs
Publication statusPublished - Jan 2000
Externally publishedYes

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Ethers
Electrochemical oxidation
Sulfides
Oxidation
Electrons
Rotating disks
Voltammetry
Cations
Nitrogen
Electrodes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "Organoheteroatom compounds having a 2-(2-pyridyl)ethyl group were synthesized and their oxidation potentials were determined by rotating disk electrode voltammetry. The oxidation potentials were found to be less positive than those of the corresponding compounds having a phenyl group in place of the pyridyl group. The dynamic coordination of the pyridyl group to the heteroatom, which stabilizes the cation radical intermediate, seems to be responsible for facilitating the electron transfer. The magnitude of the intramolecular assistance increases along with an increase in the oxidation potential of the parent compounds. This tendency can be explained in terms of the energy match between the nonbonding p orbital of the pyridyl nitrogen and the HOMO of the parent heteroatom compound.",
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T1 - Intramolecular assistance of electron transfer from heteroatom compounds. Electrochemical oxidation of 2-(2-pyridyl)ethyl-substituted ethers, sulfides, and selenides

AU - Watanabe, Mitsuru

AU - Suga, Seiji

AU - Yoshida, Jun Ichi

PY - 2000/1

Y1 - 2000/1

N2 - Organoheteroatom compounds having a 2-(2-pyridyl)ethyl group were synthesized and their oxidation potentials were determined by rotating disk electrode voltammetry. The oxidation potentials were found to be less positive than those of the corresponding compounds having a phenyl group in place of the pyridyl group. The dynamic coordination of the pyridyl group to the heteroatom, which stabilizes the cation radical intermediate, seems to be responsible for facilitating the electron transfer. The magnitude of the intramolecular assistance increases along with an increase in the oxidation potential of the parent compounds. This tendency can be explained in terms of the energy match between the nonbonding p orbital of the pyridyl nitrogen and the HOMO of the parent heteroatom compound.

AB - Organoheteroatom compounds having a 2-(2-pyridyl)ethyl group were synthesized and their oxidation potentials were determined by rotating disk electrode voltammetry. The oxidation potentials were found to be less positive than those of the corresponding compounds having a phenyl group in place of the pyridyl group. The dynamic coordination of the pyridyl group to the heteroatom, which stabilizes the cation radical intermediate, seems to be responsible for facilitating the electron transfer. The magnitude of the intramolecular assistance increases along with an increase in the oxidation potential of the parent compounds. This tendency can be explained in terms of the energy match between the nonbonding p orbital of the pyridyl nitrogen and the HOMO of the parent heteroatom compound.

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