Nonheme iron(II) complexes of macrocyclic ligands in the generation of oxoiron(IV) complexes and the catalytic epoxidation of olefins

Yumi Suh, Mi Sook Seo, Kwan Mook Kim, Youn Sang Kim, Ho Gyeom Jang, Takehiko Tosha, Teizo Kitagawa, Jinheung Kim, Wonwoo Nam

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Mononuclear nonheme oxoiron(IV) complexes bearing 15-membered macrocyclic ligands were generated from the reactions of their corresponding iron(II) complexes and iodosylbenzene (PhIO) in CH3CN. The oxoiron(IV) species were characterized with various spectroscopic techniques such as UV-vis spectrophotometer, electron paramagnetic resonance, electrospray ionization mass spectrometer, and resonance Raman spectroscopy. The oxoiron(IV) complexes were inactive in olefin epoxidation. In contrast, when iron(II) or oxoiron(IV) complexes were combined with PhIO in the presence of olefins, high yields of epoxide products were obtained. These results indicate that in addition to the oxoiron(IV) species, there must be at least one more active oxidant (e.g., FeIV-OIPh adduct or oxoiron(V) species) that effects the olefin epoxidation. We have also demonstrated that the ligand environment of iron catalysts is an important factor in controlling the catalytic activity as well as the product selectivity in the epoxidation of olefins by PhIO.

Original languageEnglish
Pages (from-to)627-633
Number of pages7
JournalJournal of Inorganic Biochemistry
Volume100
Issue number4
DOIs
Publication statusPublished - 2006 Apr 1
Externally publishedYes

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Epoxidation
Alkenes
Iron
Ligands
Bearings (structural)
Ultraviolet spectrophotometers
Electrospray ionization
Raman Spectrum Analysis
Catalyst selectivity
Epoxy Compounds
Electron Spin Resonance Spectroscopy
Mass spectrometers
Oxidants
Paramagnetic resonance
Raman spectroscopy
Catalyst activity
Catalysts

Keywords

  • Biomimetic oxidation
  • Nonheme iron complex
  • Olefin epoxidation
  • Oxoiron(IV) intermediate
  • Oxygen activation

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry

Cite this

Nonheme iron(II) complexes of macrocyclic ligands in the generation of oxoiron(IV) complexes and the catalytic epoxidation of olefins. / Suh, Yumi; Seo, Mi Sook; Kim, Kwan Mook; Kim, Youn Sang; Jang, Ho Gyeom; Tosha, Takehiko; Kitagawa, Teizo; Kim, Jinheung; Nam, Wonwoo.

In: Journal of Inorganic Biochemistry, Vol. 100, No. 4, 01.04.2006, p. 627-633.

Research output: Contribution to journalArticle

Suh, Yumi ; Seo, Mi Sook ; Kim, Kwan Mook ; Kim, Youn Sang ; Jang, Ho Gyeom ; Tosha, Takehiko ; Kitagawa, Teizo ; Kim, Jinheung ; Nam, Wonwoo. / Nonheme iron(II) complexes of macrocyclic ligands in the generation of oxoiron(IV) complexes and the catalytic epoxidation of olefins. In: Journal of Inorganic Biochemistry. 2006 ; Vol. 100, No. 4. pp. 627-633.
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AU - Kim, Youn Sang

AU - Jang, Ho Gyeom

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AB - Mononuclear nonheme oxoiron(IV) complexes bearing 15-membered macrocyclic ligands were generated from the reactions of their corresponding iron(II) complexes and iodosylbenzene (PhIO) in CH3CN. The oxoiron(IV) species were characterized with various spectroscopic techniques such as UV-vis spectrophotometer, electron paramagnetic resonance, electrospray ionization mass spectrometer, and resonance Raman spectroscopy. The oxoiron(IV) complexes were inactive in olefin epoxidation. In contrast, when iron(II) or oxoiron(IV) complexes were combined with PhIO in the presence of olefins, high yields of epoxide products were obtained. These results indicate that in addition to the oxoiron(IV) species, there must be at least one more active oxidant (e.g., FeIV-OIPh adduct or oxoiron(V) species) that effects the olefin epoxidation. We have also demonstrated that the ligand environment of iron catalysts is an important factor in controlling the catalytic activity as well as the product selectivity in the epoxidation of olefins by PhIO.

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