Kinetics of incorporation of copper(II) into meso-tetraphenylporphine in dimethylformamide. Effect of carboxylate anions

Setsuro Sugata, Yoshikazu Matsushima

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The kinetics of incorporation of copper(II) into meso-tetraphenylporphine dimethylformamide, at 30°, were dependent on the copper salts employed. The reaction was first-order in total concentration of Cu(II) perchlorate, whereas half-order in that of Cu(II) acetate. At constant Cu(II) concentration, the reaction was accelerated by the addition of acetate anion(Ac), until at a ratio [Ac]/[Cu(II)] of unity it was almost ten times faster than the reaction with Cu(II) perchlorate; an increase of the ratio past unity caused a rate decrease. From this unusual acetate dependence and effect of water content in the solvent, it was concluded that the species CuAc+ was the most reactive and the dimeric species, Cu2Ac4, was unreactive. Similar rate-concentration relationships were obtained with formate, propionate and benzoate anions. Bidentate ligands such as phthalate and phenylalaninate anions did not increase the rate.

Original languageEnglish
Pages (from-to)729-731
Number of pages3
JournalJournal of Inorganic and Nuclear Chemistry
Volume39
Issue number4
DOIs
Publication statusPublished - 1977

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Dimethylformamide
carboxylates
Anions
Copper
acetates
formic acid
Negative ions
perchlorates
anions
copper
Kinetics
unity
kinetics
Acetates
phthalates
Benzoates
Propionates
formates
Water content
moisture content

Cite this

Kinetics of incorporation of copper(II) into meso-tetraphenylporphine in dimethylformamide. Effect of carboxylate anions. / Sugata, Setsuro; Matsushima, Yoshikazu.

In: Journal of Inorganic and Nuclear Chemistry, Vol. 39, No. 4, 1977, p. 729-731.

Research output: Contribution to journalArticle

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N2 - The kinetics of incorporation of copper(II) into meso-tetraphenylporphine dimethylformamide, at 30°, were dependent on the copper salts employed. The reaction was first-order in total concentration of Cu(II) perchlorate, whereas half-order in that of Cu(II) acetate. At constant Cu(II) concentration, the reaction was accelerated by the addition of acetate anion(Ac), until at a ratio [Ac]/[Cu(II)] of unity it was almost ten times faster than the reaction with Cu(II) perchlorate; an increase of the ratio past unity caused a rate decrease. From this unusual acetate dependence and effect of water content in the solvent, it was concluded that the species CuAc+ was the most reactive and the dimeric species, Cu2Ac4, was unreactive. Similar rate-concentration relationships were obtained with formate, propionate and benzoate anions. Bidentate ligands such as phthalate and phenylalaninate anions did not increase the rate.

AB - The kinetics of incorporation of copper(II) into meso-tetraphenylporphine dimethylformamide, at 30°, were dependent on the copper salts employed. The reaction was first-order in total concentration of Cu(II) perchlorate, whereas half-order in that of Cu(II) acetate. At constant Cu(II) concentration, the reaction was accelerated by the addition of acetate anion(Ac), until at a ratio [Ac]/[Cu(II)] of unity it was almost ten times faster than the reaction with Cu(II) perchlorate; an increase of the ratio past unity caused a rate decrease. From this unusual acetate dependence and effect of water content in the solvent, it was concluded that the species CuAc+ was the most reactive and the dimeric species, Cu2Ac4, was unreactive. Similar rate-concentration relationships were obtained with formate, propionate and benzoate anions. Bidentate ligands such as phthalate and phenylalaninate anions did not increase the rate.

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