Spectroscopic Analysis on Elementary Reactions of Oxidative Polymerization of 2, 6-Xylenol Catalyzed by Copper Complex

Hiroyuki Nishide, Hiroshi Nishikawa, Eishurx Tsuchida

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Abstract

The catalytic cycle of the polymerization of 2,6-xylenol catalyzed by the copper-pyridine complex is divided into four elementary processes, the coordination of the substrate (k1), the electrontransfer from the substrate to the cupric ion (k0), the dissociation of the activated substrate (kd) and the reoxidation of the catalyst (k0). The rate constant of each elementary reaction was determined by means of the stopped-flow spectrophotometric study of the copper complex, and the detailed mechanism of the catalysis was discussed. From the comparison of rate constants (Table 1), the process involning. either ke or kd was considered to be the rate-determining step but the latter could not be measured in the present procedure. It was found that the oxygen molecule was involved in the cupric substrate complex, promoting the ke process. The rate constants were affected by the components of the solvent. Except for a few cases where solvents having coordinating ability are used, k1 and k0 increased and k0 decreased with the increasing solvent polarity.

Original languageEnglish
Pages (from-to)771-774
Number of pages4
JournalNippon Kagaku Kaishi / Chemical Society of Japan - Chemistry and Industrial Chemistry Journal
Volume1974
Issue number4
DOIs
Publication statusPublished - 1974

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Spectroscopic analysis
Copper
Polymerization
Rate constants
Substrates
Pyridine
Catalysis
Ions
Oxygen
Catalysts
Molecules
2,6-xylenol

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Spectroscopic Analysis on Elementary Reactions of Oxidative Polymerization of 2, 6-Xylenol Catalyzed by Copper Complex",
abstract = "The catalytic cycle of the polymerization of 2,6-xylenol catalyzed by the copper-pyridine complex is divided into four elementary processes, the coordination of the substrate (k1), the electrontransfer from the substrate to the cupric ion (k0), the dissociation of the activated substrate (kd) and the reoxidation of the catalyst (k0). The rate constant of each elementary reaction was determined by means of the stopped-flow spectrophotometric study of the copper complex, and the detailed mechanism of the catalysis was discussed. From the comparison of rate constants (Table 1), the process involning. either ke or kd was considered to be the rate-determining step but the latter could not be measured in the present procedure. It was found that the oxygen molecule was involved in the cupric substrate complex, promoting the ke process. The rate constants were affected by the components of the solvent. Except for a few cases where solvents having coordinating ability are used, k1 and k0 increased and k0 decreased with the increasing solvent polarity.",
author = "Hiroyuki Nishide and Hiroshi Nishikawa and Eishurx Tsuchida",
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T1 - Spectroscopic Analysis on Elementary Reactions of Oxidative Polymerization of 2, 6-Xylenol Catalyzed by Copper Complex

AU - Nishide, Hiroyuki

AU - Nishikawa, Hiroshi

AU - Tsuchida, Eishurx

PY - 1974

Y1 - 1974

N2 - The catalytic cycle of the polymerization of 2,6-xylenol catalyzed by the copper-pyridine complex is divided into four elementary processes, the coordination of the substrate (k1), the electrontransfer from the substrate to the cupric ion (k0), the dissociation of the activated substrate (kd) and the reoxidation of the catalyst (k0). The rate constant of each elementary reaction was determined by means of the stopped-flow spectrophotometric study of the copper complex, and the detailed mechanism of the catalysis was discussed. From the comparison of rate constants (Table 1), the process involning. either ke or kd was considered to be the rate-determining step but the latter could not be measured in the present procedure. It was found that the oxygen molecule was involved in the cupric substrate complex, promoting the ke process. The rate constants were affected by the components of the solvent. Except for a few cases where solvents having coordinating ability are used, k1 and k0 increased and k0 decreased with the increasing solvent polarity.

AB - The catalytic cycle of the polymerization of 2,6-xylenol catalyzed by the copper-pyridine complex is divided into four elementary processes, the coordination of the substrate (k1), the electrontransfer from the substrate to the cupric ion (k0), the dissociation of the activated substrate (kd) and the reoxidation of the catalyst (k0). The rate constant of each elementary reaction was determined by means of the stopped-flow spectrophotometric study of the copper complex, and the detailed mechanism of the catalysis was discussed. From the comparison of rate constants (Table 1), the process involning. either ke or kd was considered to be the rate-determining step but the latter could not be measured in the present procedure. It was found that the oxygen molecule was involved in the cupric substrate complex, promoting the ke process. The rate constants were affected by the components of the solvent. Except for a few cases where solvents having coordinating ability are used, k1 and k0 increased and k0 decreased with the increasing solvent polarity.

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