Synthesis, characterization, and oxygenation of bis-fenced porphyrinato iron(II) and cobalt(II) complexes

Eishun Tsuchida, Teruyuki Komatsu, Etsuo Hasegawa, Hiroyuki Nishide

研究成果: Article

45 引用 (Scopus)

抄録

The both-faces-hindered and highly symmetric complexes 5,10,15,20- tetra(2′,6′-dipivaloyl-oxyphenyl)porphyrinato-iron(II) and -cobalt(II), which have no amide residues but ester ones in the fence groups, have been synthesized. The iron(II) complex formed stable and reversible dioxygen adducts in toluene at 25 °C. The half-life for irreversible oxidation is longer than 1 d. The ligation properties for this complex with imidazole derivatives or dioxygen have been determined and compared to those of one-face-hindered porphyrinatoiron complexes. The bulky groups on both sides of the macrocycle decrease the binding constants for imidazole and for dioxygen. The binding characteristics of an imidazole derivative, which is sterically restrained by the bulky groups, have been clarified by Mössbauer and i.r. spectroscopic measurements. A kinetic study of dioxygen association and dissociation suggests that the low oxygen affinity is brought about primarily by the high rate of ligand dissociation.

元の言語English
ページ(範囲)2713-2718
ページ数6
ジャーナルJournal of the Chemical Society, Dalton Transactions
発行部数9
DOI
出版物ステータスPublished - 1990

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Oxygenation
Cobalt
Iron
Oxygen
Derivatives
Fences
Toluene
Amides
Esters
Association reactions
Ligands
Oxidation
Kinetics
imidazole

ASJC Scopus subject areas

  • Chemistry(all)

これを引用

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abstract = "The both-faces-hindered and highly symmetric complexes 5,10,15,20- tetra(2′,6′-dipivaloyl-oxyphenyl)porphyrinato-iron(II) and -cobalt(II), which have no amide residues but ester ones in the fence groups, have been synthesized. The iron(II) complex formed stable and reversible dioxygen adducts in toluene at 25 °C. The half-life for irreversible oxidation is longer than 1 d. The ligation properties for this complex with imidazole derivatives or dioxygen have been determined and compared to those of one-face-hindered porphyrinatoiron complexes. The bulky groups on both sides of the macrocycle decrease the binding constants for imidazole and for dioxygen. The binding characteristics of an imidazole derivative, which is sterically restrained by the bulky groups, have been clarified by M{\"o}ssbauer and i.r. spectroscopic measurements. A kinetic study of dioxygen association and dissociation suggests that the low oxygen affinity is brought about primarily by the high rate of ligand dissociation.",
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AU - Tsuchida, Eishun

AU - Komatsu, Teruyuki

AU - Hasegawa, Etsuo

AU - Nishide, Hiroyuki

PY - 1990

Y1 - 1990

N2 - The both-faces-hindered and highly symmetric complexes 5,10,15,20- tetra(2′,6′-dipivaloyl-oxyphenyl)porphyrinato-iron(II) and -cobalt(II), which have no amide residues but ester ones in the fence groups, have been synthesized. The iron(II) complex formed stable and reversible dioxygen adducts in toluene at 25 °C. The half-life for irreversible oxidation is longer than 1 d. The ligation properties for this complex with imidazole derivatives or dioxygen have been determined and compared to those of one-face-hindered porphyrinatoiron complexes. The bulky groups on both sides of the macrocycle decrease the binding constants for imidazole and for dioxygen. The binding characteristics of an imidazole derivative, which is sterically restrained by the bulky groups, have been clarified by Mössbauer and i.r. spectroscopic measurements. A kinetic study of dioxygen association and dissociation suggests that the low oxygen affinity is brought about primarily by the high rate of ligand dissociation.

AB - The both-faces-hindered and highly symmetric complexes 5,10,15,20- tetra(2′,6′-dipivaloyl-oxyphenyl)porphyrinato-iron(II) and -cobalt(II), which have no amide residues but ester ones in the fence groups, have been synthesized. The iron(II) complex formed stable and reversible dioxygen adducts in toluene at 25 °C. The half-life for irreversible oxidation is longer than 1 d. The ligation properties for this complex with imidazole derivatives or dioxygen have been determined and compared to those of one-face-hindered porphyrinatoiron complexes. The bulky groups on both sides of the macrocycle decrease the binding constants for imidazole and for dioxygen. The binding characteristics of an imidazole derivative, which is sterically restrained by the bulky groups, have been clarified by Mössbauer and i.r. spectroscopic measurements. A kinetic study of dioxygen association and dissociation suggests that the low oxygen affinity is brought about primarily by the high rate of ligand dissociation.

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