Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature

J. Kaizer, Eric J. Klinker, Na Young Oh, Jan Uwe Rohde, Woon Ju Song, Audria Stubna, Jinheung Kim, Eckard Münck, Wonwoo Nam, Lawrence Que

Research output: Contribution to journalArticle

451 Citations (Scopus)

Abstract

Nonheme oxoiron(IV) complexes of two pentadentate ligands, N4Py (N,N-bis(2-pyridylmethyl)-bis(2-pyridyl)methylamine) and Bn-tpen (N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier. However, unlike the TPA complex, the pentadentate complexes have a considerable lifetime at room temperature. This greater thermal stability has allowed the hydroxylation of alkanes with C-H bonds as strong as 99.3 kcal/mol to be observed at room temperature. Furthermore, a large deuterium KIE value is found in the oxidation of ethylbenzene. These observations lend strong credence to postulated mechanisms of mononuclear nonheme iron enzymes that invoke the intermediacy of oxoiron(IV) species.

Original languageEnglish
Pages (from-to)472-473
Number of pages2
JournalJournal of the American Chemical Society
Volume126
Issue number2
DOIs
Publication statusPublished - Jan 21 2004

Fingerprint

ethylenediamine
Cyclohexane
Hydroxylation
Temperature
Alkanes
Ethylbenzene
Deuterium
Paraffins
Amines
Thermodynamic stability
Iron
Enzymes
Hot Temperature
Ligands
Oxidation
bis(2-pyridyl)methylamine
ethylbenzene
tris(2-pyridylmethyl)amine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature. / Kaizer, J.; Klinker, Eric J.; Oh, Na Young; Rohde, Jan Uwe; Song, Woon Ju; Stubna, Audria; Kim, Jinheung; Münck, Eckard; Nam, Wonwoo; Que, Lawrence.

In: Journal of the American Chemical Society, Vol. 126, No. 2, 21.01.2004, p. 472-473.

Research output: Contribution to journalArticle

Kaizer, J, Klinker, EJ, Oh, NY, Rohde, JU, Song, WJ, Stubna, A, Kim, J, Münck, E, Nam, W & Que, L 2004, 'Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature', Journal of the American Chemical Society, vol. 126, no. 2, pp. 472-473. https://doi.org/10.1021/ja037288n
Kaizer, J. ; Klinker, Eric J. ; Oh, Na Young ; Rohde, Jan Uwe ; Song, Woon Ju ; Stubna, Audria ; Kim, Jinheung ; Münck, Eckard ; Nam, Wonwoo ; Que, Lawrence. / Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 2. pp. 472-473.
@article{043159719ddb41299d21227e3c35608f,
title = "Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature",
abstract = "Nonheme oxoiron(IV) complexes of two pentadentate ligands, N4Py (N,N-bis(2-pyridylmethyl)-bis(2-pyridyl)methylamine) and Bn-tpen (N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier. However, unlike the TPA complex, the pentadentate complexes have a considerable lifetime at room temperature. This greater thermal stability has allowed the hydroxylation of alkanes with C-H bonds as strong as 99.3 kcal/mol to be observed at room temperature. Furthermore, a large deuterium KIE value is found in the oxidation of ethylbenzene. These observations lend strong credence to postulated mechanisms of mononuclear nonheme iron enzymes that invoke the intermediacy of oxoiron(IV) species.",
author = "J. Kaizer and Klinker, {Eric J.} and Oh, {Na Young} and Rohde, {Jan Uwe} and Song, {Woon Ju} and Audria Stubna and Jinheung Kim and Eckard M{\"u}nck and Wonwoo Nam and Lawrence Que",
year = "2004",
month = "1",
day = "21",
doi = "10.1021/ja037288n",
language = "English",
volume = "126",
pages = "472--473",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Nonheme FeIVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature

AU - Kaizer, J.

AU - Klinker, Eric J.

AU - Oh, Na Young

AU - Rohde, Jan Uwe

AU - Song, Woon Ju

AU - Stubna, Audria

AU - Kim, Jinheung

AU - Münck, Eckard

AU - Nam, Wonwoo

AU - Que, Lawrence

PY - 2004/1/21

Y1 - 2004/1/21

N2 - Nonheme oxoiron(IV) complexes of two pentadentate ligands, N4Py (N,N-bis(2-pyridylmethyl)-bis(2-pyridyl)methylamine) and Bn-tpen (N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier. However, unlike the TPA complex, the pentadentate complexes have a considerable lifetime at room temperature. This greater thermal stability has allowed the hydroxylation of alkanes with C-H bonds as strong as 99.3 kcal/mol to be observed at room temperature. Furthermore, a large deuterium KIE value is found in the oxidation of ethylbenzene. These observations lend strong credence to postulated mechanisms of mononuclear nonheme iron enzymes that invoke the intermediacy of oxoiron(IV) species.

AB - Nonheme oxoiron(IV) complexes of two pentadentate ligands, N4Py (N,N-bis(2-pyridylmethyl)-bis(2-pyridyl)methylamine) and Bn-tpen (N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier. However, unlike the TPA complex, the pentadentate complexes have a considerable lifetime at room temperature. This greater thermal stability has allowed the hydroxylation of alkanes with C-H bonds as strong as 99.3 kcal/mol to be observed at room temperature. Furthermore, a large deuterium KIE value is found in the oxidation of ethylbenzene. These observations lend strong credence to postulated mechanisms of mononuclear nonheme iron enzymes that invoke the intermediacy of oxoiron(IV) species.

UR - http://www.scopus.com/inward/record.url?scp=0347717615&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0347717615&partnerID=8YFLogxK

U2 - 10.1021/ja037288n

DO - 10.1021/ja037288n

M3 - Article

C2 - 14719937

AN - SCOPUS:0347717615

VL - 126

SP - 472

EP - 473

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -