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 language | English |
|---|---|
| Pages (from-to) | 627-633 |
| Number of pages | 7 |
| Journal | Journal of Inorganic Biochemistry |
| Volume | 100 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - 2006 Apr 1 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Nonheme iron(II) complexes of macrocyclic ligands in the generation of oxoiron(IV) complexes and the catalytic epoxidation of olefins
AU - Suh, Yumi
AU - Seo, Mi Sook
AU - Kim, Kwan Mook
AU - Kim, Youn Sang
AU - Jang, Ho Gyeom
AU - Tosha, Takehiko
AU - Kitagawa, Teizo
AU - Kim, Jinheung
AU - Nam, Wonwoo
PY - 2006/4/1
Y1 - 2006/4/1
N2 - 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.
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.
KW - Biomimetic oxidation
KW - Nonheme iron complex
KW - Olefin epoxidation
KW - Oxoiron(IV) intermediate
KW - Oxygen activation
UR - http://www.scopus.com/inward/record.url?scp=33645871306&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33645871306&partnerID=8YFLogxK
U2 - 10.1016/j.jinorgbio.2005.12.013
DO - 10.1016/j.jinorgbio.2005.12.013
M3 - Article
C2 - 16458358
AN - SCOPUS:33645871306
VL - 100
SP - 627
EP - 633
JO - Journal of Inorganic Biochemistry
JF - Journal of Inorganic Biochemistry
SN - 0162-0134
IS - 4
ER -