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 G. Jang; Takehiko Tosha; Teizo Kitagawa; Jinheung Kim; Wonwoo Nam

doi:10.1016/j.jinorgbio.2005.12.013

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 G. Jang, Takehiko Tosha, Teizo Kitagawa, Jinheung Kim, Wonwoo Nam

Research output: Contribution to journal › Review article › peer-review

61 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., Fe^IV-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	https://doi.org/10.1016/j.jinorgbio.2005.12.013
Publication status	Published - 2006 Apr

Bibliographical note

Funding Information:
This work was supported by the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.), the SRC/ERC program of MOST/KOSEF (R11-2005-008-00000-0 to J.K., Y.S.K., and K.M.K.), and the Korea Research Foundation (KRF-2005-217-C00006 to M.S.S.).

Keywords

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

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry

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10.1016/j.jinorgbio.2005.12.013

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@article{0a504b28378149e09657116954d99506,

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

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.",

keywords = "Biomimetic oxidation, Nonheme iron complex, Olefin epoxidation, Oxoiron(IV) intermediate, Oxygen activation",

author = "Yumi Suh and Seo, {Mi Sook} and Kim, {Kwan Mook} and Kim, {Youn Sang} and Jang, {Ho G.} and Takehiko Tosha and Teizo Kitagawa and Jinheung Kim and Wonwoo Nam",

note = "Funding Information: This work was supported by the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.), the SRC/ERC program of MOST/KOSEF (R11-2005-008-00000-0 to J.K., Y.S.K., and K.M.K.), and the Korea Research Foundation (KRF-2005-217-C00006 to M.S.S.). ",

year = "2006",

month = apr,

doi = "10.1016/j.jinorgbio.2005.12.013",

language = "English",

volume = "100",

pages = "627--633",

journal = "Journal of Inorganic Biochemistry",

issn = "0162-0134",

publisher = "Elsevier Inc.",

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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 G.

AU - Tosha, Takehiko

AU - Kitagawa, Teizo

AU - Kim, Jinheung

AU - Nam, Wonwoo

N1 - Funding Information: This work was supported by the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.), the SRC/ERC program of MOST/KOSEF (R11-2005-008-00000-0 to J.K., Y.S.K., and K.M.K.), and the Korea Research Foundation (KRF-2005-217-C00006 to M.S.S.).

PY - 2006/4

Y1 - 2006/4

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

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U2 - 10.1016/j.jinorgbio.2005.12.013

DO - 10.1016/j.jinorgbio.2005.12.013

M3 - Review article

C2 - 16458358

AN - SCOPUS:33645871306

SN - 0162-0134

VL - 100

SP - 627

EP - 633

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

IS - 4

ER -

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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