Electron-transfer Reactions between Cobalt (III)-Partially-quaternized-Poly (4-vinylpyridine) Complexes and Ferrous EDTA

Eishun Tsuchida, Hiroyuki Nishide, Tetsu Ohkawa, Yoshimi Kurimura

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Abstract

In order to study the electrostatic effect of polymer complex on its reactivity, the rate constants and the activation parameters for the electron-transfer reactions of cis-[Co(III) (en)2L Cl] • Cl2 were determined (L = QPVP: partially-quaternized-poly(4-vinylpyridine) by benzylchloride; PVP: poly (4-vinylpyridine); Py: pyridine). The reduction rates of Co(III)-polymer complexes by ferrous sulfate were almost the same as that of Co(III)-Py complex (Table 2). The rate constants of the reduction by Fe(II)EDTA2– decreased in the following order: Co(III)-QPVP >Co(III)-PVP>Co(III)-Py (Table 3). An increase in degree of coordination and in that of quaternization brought about an increase in reactivity of QPVP complex (Fig. 1). The acceleration for polymer complex was found to be due to a decrease in activation enthalpy and an increase in activation entropy. These results were interpreted in terms of the electrostatic attraction between FeEDTA2– and polymer metal complex, viz., a polycation. For QPVP complex the electrostatic effect was considered to be more pronounced by pyridinium cation situated on QPVP chain.

Original languageEnglish
Pages (from-to)1768-1770
Number of pages3
JournalNippon Kagaku Kaishi
Volume1974
Issue number9
DOIs
Publication statusPublished - 1974

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Ethylenediaminetetraacetic acid
Cobalt
Edetic Acid
Polymers
Electrostatics
ferrous sulfate
Electrons
Chemical activation
Rate constants
Coordination Complexes
Metal complexes
Pyridine
Cations
Enthalpy
Entropy
Positive ions
poly(4-vinylpyridine)

ASJC Scopus subject areas

  • Chemistry(all)

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Electron-transfer Reactions between Cobalt (III)-Partially-quaternized-Poly (4-vinylpyridine) Complexes and Ferrous EDTA. / Tsuchida, Eishun; Nishide, Hiroyuki; Ohkawa, Tetsu; Kurimura, Yoshimi.

In: Nippon Kagaku Kaishi, Vol. 1974, No. 9, 1974, p. 1768-1770.

Research output: Contribution to journalArticle

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AU - Kurimura, Yoshimi

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AB - In order to study the electrostatic effect of polymer complex on its reactivity, the rate constants and the activation parameters for the electron-transfer reactions of cis-[Co(III) (en)2L Cl] • Cl2 were determined (L = QPVP: partially-quaternized-poly(4-vinylpyridine) by benzylchloride; PVP: poly (4-vinylpyridine); Py: pyridine). The reduction rates of Co(III)-polymer complexes by ferrous sulfate were almost the same as that of Co(III)-Py complex (Table 2). The rate constants of the reduction by Fe(II)EDTA2– decreased in the following order: Co(III)-QPVP >Co(III)-PVP>Co(III)-Py (Table 3). An increase in degree of coordination and in that of quaternization brought about an increase in reactivity of QPVP complex (Fig. 1). The acceleration for polymer complex was found to be due to a decrease in activation enthalpy and an increase in activation entropy. These results were interpreted in terms of the electrostatic attraction between FeEDTA2– and polymer metal complex, viz., a polycation. For QPVP complex the electrostatic effect was considered to be more pronounced by pyridinium cation situated on QPVP chain.

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