A Synthetic High-Spin Oxoiron(IV) Complex: Generation, Spectroscopic Characterization, and Reactivity

被引：222

作者：

England, Jason ^{[2
,3
]}

Martinho, Marlene ^{[1
]}

Farquhar, Erik R. ^{[2
,3
]}

Frisch, Jonathan R. ^{[2
,3
]}

Bominaar, Emile L. ^{[1
]}

Muenck, Eckard ^{[1
]}

Que, Lawrence, Jr. ^{[2
,3
]}

机构：

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

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

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2009年 / 48卷 / 20期

关键词：

bioinorganic chemistry; enzyme models; high-valent compounds; iron; nonheme iron complexes; TAURINE/ALPHA-KETOGLUTARATE DIOXYGENASE; FE-IV=O; ELECTRONIC-STRUCTURES; ALKANE HYDROXYLATION; FE(IV) INTERMEDIATE; ESCHERICHIA-COLI; NONHEME; IRON; LIGAND; OXO;

D O I：

10.1002/anie.200900863

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

High versus low: The high-yield generation of a synthetic high-spin oxoiron(IV) complex, [FeIV(O)(TMG3tren)]2+ (see picture, TMG3tren = 1,1,1-tris{2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl} amine), has been achieved by using the very bulky tetradentate TMG 3tren ligand, in order to both sterically protect the oxoiron (IV) moiety and enforce a trigonal bipyramidal geometry at the iron center, for which an S=2 ground state is favored. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

收藏

页码：3622 / 3626

页数：5

相关论文

共 36 条

[1] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].

ADDISON, AW ;

RAO, TN ;

REEDIJK, J ;

VANRIJN, J ;

VERSCHOOR, GC .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356

[2]

Banse F., 2008, ANGEW CHEM, V120, P7172

[3] The role of equatorial and axial ligands in promoting the activity of non-heme oxidoiron(IV) catalysts in alkane hydroxylation [J].

Bernasconi, Leonardo ;

Louwerse, Manuel J. ;

Baerends, Evert Jan .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2007, (19) :3023-3033

[4] Electronic structure and spectroscopy of "superoxidized" iron centers in model systems: theoretical and experimental trends [J].

Berry, John F. ;

George, Serena DeBeer ;

Neese, Frank .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (30) :4361-4374

[5]

CHIVUKULA SV, 2007, P NATL ACAD SCI USA, V104, P19181

[6] 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

[7] 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

[8] Direct spectroscopic evidence for a high-spin Fe(IV) intermediate in tyrosine hydroxylase [J].

Eser, Bekir E. ;

Barr, Eric W. ;

Frantorn, Patrick A. ;

Saleh, Lana ;

Bollinger, J. Martin, Jr. ;

Krebs, Carsten ;

Fitzpatrick, Paul F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (37) :11334-+

[9] Two interconverting Fe(IV) intermediates in aliphatic chlorination by the halogenase CytC3 [J].

Galonic, Danica P. ;

Barr, Eric W. ;

Walsh, Christopher T. ;

Bollinger, J. Martin, Jr. ;

Krebs, Carsten .

NATURE CHEMICAL BIOLOGY, 2007, 3 (02) :113-116

[10] Phenolate Hydroxylation in a Bis(μ-oxo)dicopper(III) Complex: Lessons from the Guanidine/Amine Series [J].

Herres-Pawlis, Sonia ;

Verma, Pratilk ;

Haase, Roxana ;

Kang, Peng ;

Lyons, Christopher T. ;

Wasinger, Erik C. ;

Floerke, Ulrich ;

Henkel, Gerald ;

Stack, T. Daniel P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (03) :1154-1169

← 1 2 3 4 →