A Combined NRVS and DFT Study of FeIV=O Model Complexes: A Diagnostic Method for the Elucidation of Non-Heme Iron Enzyme Intermediates

被引：41

作者：

Bell, Caleb B., III ^{[1
]}

Wong, Shaun D. ^{[1
]}

Xiao, Yuming ^{[2
,3
]}

Klinker, Eric J.

Tenderholt, Adam L. ^{[1
]}

Smith, Matt C. ^{[2
,3
]}

Rohde, Jan-Uwe

Que, Lawrence, Jr.

Cramer, Stephen P. ^{[2
,3
]}

Solomon, Edward I. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Univ Calif Davis, Dept Appl Sci, Davis, CA 95616 USA

[3] Lawrence Berkeley Natl Lab, Phys Biosci Div, Berkeley, CA USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 47期

关键词：

bioinorganic chemistry; iron; nuclear vibrational resonance spectroscopy; X-ray absorption spectroscopy;

D O I：

10.1002/anie.200803740

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Figure Presented) In the swing of things: FeIV=O biomimetic model complexes (see picture, Fe green, O red, N blue, C black) have been characterized using nuclear vibrational resonance spectroscopy. Systematic trends in the low-energy region reflect equatorial and axial bonding differences that relate to differences in reactivity. These trends have been computationally extended to predict the spectra of putative FeIV=O intermediates in non-heme iron enzymes. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

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收藏

页码：9071 / 9074

页数：4

相关论文

共 29 条

[1] Phonon-assisted Mossbauer effect: The vibrational density of states of myoglobin [J].

Achterhold, K ;

Sturhahn, W ;

Alp, EE ;

Parak, FG .

HYPERFINE INTERACTIONS, 2002, 141 (1-4) :3-12

[2] NUCLEAR RESONANT SCATTERING BEAMLINE AT THE ADVANCED PHOTON SOURCE [J].

ALP, EE ;

MOONEY, TM ;

TOELLNER, T ;

STURHAHN, W .

HYPERFINE INTERACTIONS, 1994, 90 (1-4) :323-334

[3] Nuclear resonance vibrational spectroscopy (NRVS) of Fe-S model compounds, Fe-S proteins, and nitrogenase [J].

Cramer, Stephen P. ;

Xiao, Yuming ;

Wang, Hongxin ;

Guo, Yisong ;

Smith, Matt C. .

HYPERFINE INTERACTIONS, 2006, 170 (1-3) :47-54

[4] Spectroscopic and quantum chemical characterization of the electronic structure and bonding in a non-heme FeIV=O complex [J].

Decker, A ;

Rohde, JU ;

Que, L ;

Solomon, EI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (17) :5378-5379

[5] Spectroscopic and quantum chemical studies on low-spin FeIV=O complexes:: Fe-O bonding and its contributions to reactivity [J].

Decker, Andrea ;

Rohde, Jan-Uwe ;

Klinker, Eric J. ;

Wong, Shaun D. ;

Que, Lawrence, Jr. ;

Solomon, Edward I. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (51) :15983-15996

[6] Axial ligand effects on the geometric and electronic structures of nonheme Oxoiron(IV) complexes [J].

Jackson, Timothy A. ;

Rohde, Jan-Uwe ;

Seo, Mi Sook ;

Sastri, Chivukula V. ;

DeHont, Raymond ;

Stubna, Audria ;

Ohta, Takehiro ;

Kitagawa, Teizo ;

Munck, Eckard ;

Nam, Wonwoo ;

Que, Lawrence, Jr. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (37) :12394-12407

[7] Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature [J].

Kaizer, J ;

Klinker, EJ ;

Oh, NY ;

Rohde, JU ;

Song, WJ ;

Stubna, A ;

Kim, J ;

Münck, E ;

Nam, W ;

Que, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (02) :472-473

[8]

Klinker E. J., 2005, ANGEW CHEM, V117, P3756

[9] Structures of nonheme oxoiron(IV) complexes from x-ray crystallography, NMR spectroscopy, and DFT calculations [J].

Klinker, EJ ;

Kaizer, J ;

Brennessel, WW ;

Woodrum, NL ;

Cramer, CJ ;

Que, L .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (24) :3690-3694

[10] Quantitative vibrational dynamics of iron in nitrosyl porphyrins [J].

Leu, BM ;

Zgierski, MZ ;

Wyllie, GRA ;

Scheidt, WR ;

Sturhahn, W ;

Alp, EE ;

Durbin, SM ;

Sage, JT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (13) :4211-4227