Chemical and spectroscopic evidence for an FeV-Oxo complex

被引：373

作者：

Tiago de Oliveira, Filipe

Chanda, Arani

Banerjee, Deboshri

Shan, Xiaopeng

Mondal, Sujit

Que, Lawrence, Jr. ^{[1
]}

Bominaar, Emile L.

Muenck, Eckard

Collins, Terrence J.

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA

[3] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA

来源：

SCIENCE | 2007年 / 315卷 / 5813期

关键词：

D O I：

10.1126/science.1133417

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Iron(V)-oxo species have been proposed as key reactive intermediates in the catalysis of oxygen-activating enzymes and synthetic catalysts. Here, we report the synthesis of [Fe(TAML)(O)](-) in nearly quantitative yield, where TAML is a macrocyclic tetraamide ligand. Mass spectrometry, Mossbauer, electron paramagnetic resonance, and x-ray absorption spectroscopies, as well as reactivity studies and density functional theory calculations show that this long-lived (hours at -60 degrees C) intermediate is a spin S=1/2 iron(V)-oxo complex. Iron-TAML systems have proven to be efficient catalysts in the decomposition of numerous pollutants by hydrogen peroxide, and the species we characterized is a likely reactive intermediate in these reactions.

引用

收藏

页码：835 / 838

页数：4

相关论文

共 18 条

[1] The geometric and electronic structure of [(cyclam-acetato)Fe(N)+]:: A genuine iron(V) species with a ground-state spin S=1/2 [J].

Aliaga-Alcalde, N ;

George, SD ;

Mienert, B ;

Bill, E ;

Wieghardt, K ;

Neese, F .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (19) :2908-2912

[2] Green oxidation catalysis for rapid deactivation of bacterial spores [J].

Banerjee, Deboshri ;

Markley, Andrew L. ;

Yano, Toshihiro ;

Ghosh, Anindya ;

Berget, Peter B. ;

Minkley, Edwin G., Jr. ;

Khetan, Sushil K. ;

Collins, Terrence J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (24) :3974-3977

[3] Designing ligands to achieve robust oxidation catalysts. Iron based systems [J].

Bartos, MJ ;

Gordon-Wylie, SW ;

Fox, BG ;

Wright, LJ ;

Weintraub, ST ;

Kauffmann, KE ;

Munck, E ;

Kostka, KL ;

Uffelman, ES ;

Rickard, CEF ;

Noon, KR ;

Collins, TJ .

COORDINATION CHEMISTRY REVIEWS, 1998, 174 :361-390

[4] ACCURATE EMPIRICAL SPIN-ORBIT-COUPLING PARAMETERS ZETA(ND) FOR GASEOUS ND(Q) TRANSITION-METAL IONS - THE PARAMETRICAL MULTIPLET TERM MODEL [J].

BENDIX, J ;

BRORSON, M ;

SCHAFFER, CE .

INORGANIC CHEMISTRY, 1993, 32 (13) :2838-2849

[5] A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450 [J].

Bukowski, MR ;

Koehntop, KD ;

Stubna, A ;

Bominaar, EL ;

Halfen, JA ;

Münck, E ;

Nam, W ;

Que, L .

SCIENCE, 2005, 310 (5750) :1000-1002

[6] High-valent iron complexes with tetraamido macrocyclic ligands: Structures, Mossbauer spectroscopy, and DFT calculations [J].

Chanda, Arani ;

Popescu, Delia-Laura ;

de Oliveira, Filipe Tiago ;

Bominaar, Emile L. ;

Ryabov, Alexander D. ;

Munck, Eckard ;

Collins, Terrence J. .

JOURNAL OF INORGANIC BIOCHEMISTRY, 2006, 100 (04) :606-619

[7] Dioxygen activation at mononuclear nonheme iron active sites: Enzymes, models, and intermediates [J].

Costas, M ;

Mehn, MP ;

Jensen, MP ;

Que, L .

CHEMICAL REVIEWS, 2004, 104 (02) :939-986

[8] Spectroscopy and electronic structures of mono- and binuclear high-valent non-heme iron-oxo systems [J].

Decker, Andrea ;

Clay, Michael D. ;

Solomon, Edward I. .

JOURNAL OF INORGANIC BIOCHEMISTRY, 2006, 100 (04) :697-706

[9] Structure and chemistry of cytochrome P450 [J].

Denisov, IG ;

Makris, TM ;

Sligar, SG ;

Schlichting, I .

CHEMICAL REVIEWS, 2005, 105 (06) :2253-2277

[10] Catalytically active μ-oxodiiron(IV) oxidants from iron(III) and dioxygen [J].

Ghosh, A ;

de Oliveira, FT ;

Yano, T ;

Nishioka, T ;

Beach, ES ;

Kinoshita, I ;

Münck, E ;

Ryabov, AD ;

Horwitz, CP ;

Collins, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (08) :2505-2513