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

Eishun Tsuchida, Teruyuki Komatsu, Etsuo Hasegawa, Hiroyuki Nishide

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45 Citations (Scopus)

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 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.

Original languageEnglish
Pages (from-to)2713-2718
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number9
DOIs
Publication statusPublished - 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)

Cite this

Synthesis, characterization, and oxygenation of bis-fenced porphyrinato iron(II) and cobalt(II) complexes. / Tsuchida, Eishun; Komatsu, Teruyuki; Hasegawa, Etsuo; Nishide, Hiroyuki.

In: Journal of the Chemical Society, Dalton Transactions, No. 9, 1990, p. 2713-2718.

Research output: Contribution to journalArticle

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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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