A mixed-valent, Fe(II)Fe(I), diiron complex reproduces the unique rotated state of the [FeFe]hydrogenase active site

被引：256

作者：

Liu, Tianbiao ^{[1
]}

Darensbourg, Marcetta Y. ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77845 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 22期

关键词：

D O I：

10.1021/ja071851a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The fully reversible (FeFeI)-Fe-I -> (FeFeII)-Fe-I couple of an N-heterocyclic carbene dinuclear (FeFeI)-Fe-I complex, (mu-pdt)[Fe-I(CO)(2)(PMe3)][Fe-I(CO)(2)(IMes)], complex D, has led to the isolation of the mixed-valent cationic complex D-ox as a biomimetic of the 2Fe2S subsite of the oxidized H cluster in [FeFe]hydrogenase. During the review of this submission a second complex was reported. As compared to complex D, a remarkable reorientation of the IMes NHC ligand enables the (mu-pdt)[Fe(CO)(2)(PMe3)][Fe(CO)(2)(IMes)](+) cation, D-ox, to exist as a "rotated" structure, with structural and spectroscopic similarities to the diiron unit of H-as isolated or H-ox. The structural makeup of the model includes an Fe-Fe distance that matches that of the enzyme, a semi-bridging CO group, and a pseudo-octahedral iron with open site blocked by a strategically positioned arene group from the IMes-NHC carbene ligand.

引用

页码：7008 / +

页数：3

共 17 条

[1] Reversible carbon monoxide binding and inhibition at the active site of the Fe-only hydrogenase [J].

Bennett, B ;

Lemon, BJ ;

Peters, JW .

BIOCHEMISTRY, 2000, 39 (25) :7455-7460

[2] Electron transfer at a dithiolate-bridged diiron assembly: Electrocatalytic hydrogen evolution [J].

Borg, SJ ;

Behrsing, T ;

Best, SP ;

Razavet, M ;

Liu, XM ;

Pickett, CJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (51) :16988-16999

[3] N-heterocyclic carbene ligands as cyanide mimics in diiron models of the all-iron hydrogenase active site [J].

Capon, JF ;

El Hassnaoui, S ;

Gloaguen, F ;

Schollhammer, P ;

Talarmin, J .

ORGANOMETALLICS, 2005, 24 (09) :2020-2022

[4] The organometallic active site of [Fe]hydrogenase: Models and entatic states [J].

Darensbourg, MY ;

Lyon, EJ ;

Zhao, X ;

Georgakaki, IP .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2003, 100 (07) :3683-3688

[5] Diruthenium dithiolato cyanides: Basic reactivity studies and a post hoc examination of nature's choice of Fe versus Ru for hydrogenogenesis [J].

Justice, AK ;

Linck, RC ;

Rauchfuss, TB .

INORGANIC CHEMISTRY, 2006, 45 (06) :2406-2412

[6]

JUSTICE AK, 2007, CHEM COMMUN

[7] Coordination sphere flexibility of active-site models for Fe-only hydrogenase: Studies in intra- and intermolecular diatomic ligand exchange [J].

Lyon, EJ ;

Georgakaki, IP ;

Reibenspies, JH ;

Darensbourg, MY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (14) :3268-3278

[8] A novel FeS cluster in Fe-only hydrogenases [J].

Nicolet, Y ;

Lemon, BJ ;

Fontecilla-Camps, JC ;

Peters, JW .

TRENDS IN BIOCHEMICAL SCIENCES, 2000, 25 (03) :138-143

[9] Crystallographic and FTIR spectroscopic evidence of changes in Fe coordination upon reduction of the active site of the Fe-only hydrogenase from Desulfovibrio desulfuricans [J].

Nicolet, Y ;

de Lacey, AL ;

Vernède, X ;

Fernandez, VM ;

Hatchikian, EC ;

Fontecilla-Camps, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (08) :1596-1601

[10] Electronic structure of the H cluster in [Fe]-hydrogenases [J].

Popescu, CV ;

Münck, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (34) :7877-7884

← 1 2 →