All-iron hydrogenase: synthesis, structure and properties of {2Fe3S}-assemblies related to the di-iron sub-site of the H-cluster

被引：126

作者：

Razavet, M ^{[1
]}

Davies, SC ^{[1
]}

Hughes, DL ^{[1
]}

Barclay, JE ^{[1
]}

Evans, DJ ^{[1
]}

Fairhurst, SA ^{[1
]}

Liu, XM ^{[1
]}

Pickett, CJ ^{[1
]}

机构：

[1] John Innes Ctr Plant Sci Res, Dept Biol Chem, Norwich NR4 7UH, Norfolk, England

来源：

DALTON TRANSACTIONS | 2003年 / 04期

关键词：

D O I：

10.1039/b209690k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Tripodal dithiolate thioether ligands MeC(CH2SH)(2)CH2SR (R = Me or Ph) provide a route to {2Fe3S}-complexes and syntheses are described. X-Ray crystal structures for two {2Fe3S}-pentacarbonyl derivatives and that for the first carbonyl cyanide are reported, together with temperature dependent H-1-NMR, Mossbauer, FTIR and redox potential data. The NMR data establish fluctionality associated with inversion at the thioether sulfur in the carbonyl complexes. The Mossbauer data affirm that the coordination environment of the two iron atoms in a dicyanide bridging carbonyl intermediate are differentiated. Bridging carbonyl intermediates have been structurally and spectroscopically identified in resting and CO inhibited forms of the sub-site of all-iron hydrogenases; the observation of a thermally unstable {2Fe3S}-bridging carbonyl intermediate is discussed in this context.

引用

页码：586 / 595

页数：10

共 42 条

[1]

*AD SCI PLC, 1999, GNMR VER 4 1

[2] DINITROGEN COMPLEXES OF TUNGSTEN WITH BULKY PHOSPHINE CO-LIGANDS - PREPARATION AND CRYSTAL-STRUCTURES OF [(W(N2)2(PET2PH)3)2(MU-N2)], TRANS-[W(N2)2(PET2PH)4].C4H8O, AND "[W(ETA-6-C6H5PPRN2)(N-2)(PPRN2PH)2] AND THEIR REACTIONS TO GIVE HYDRAZINE OR AMMONIA [J].

ANDERSON, SN ;

RICHARDS, RL ;

HUGHES, DL .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (02) :245-252

[3]

[Anonymous], 1992, INT TABLES XRAY CRYS, VC, p[500, 219, 193]

[4] DFT investigation of structural, electronic, and catalytic properties of diiron complexes related to the [2Fe]H subcluster of Fe-only hydrogenases [J].

Bruschi, M ;

Fantucci, P ;

De Gioia, L .

INORGANIC CHEMISTRY, 2002, 41 (06) :1421-1429

[5] Modeling the active sites in metalloenzymes. 3. Density functional calculations on models for [Fe]-hydrogenase: Structures and vibrational frequencies of the observed redox forms and the reaction mechanism at the diiron active center [J].

Cao, ZX ;

Hall, MB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (16) :3734-3742

[6] TRANSITION-METAL BINDING-SITES AND LIGAND PARAMETERS [J].

CHATT, J ;

KAN, CT ;

LEIGH, GJ ;

PICKETT, CJ ;

STANLEY, DR .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1980, (10) :2032-2038

[7] Infrared studies of the CO-inhibited form of the Fe-only hydrogenase from Clostridium pasteurianum I:: Examination of its light sensitivity at cryogenic temperatures [J].

Chen, ZJ ;

Lemon, BJ ;

Huang, S ;

Swartz, DJ ;

Peters, JW ;

Bagley, KA .

BIOCHEMISTRY, 2002, 41 (06) :2036-2043

[8] 2-ELECTRON TRANSFER CATALYSIS OF CARBON-MONOXIDE EXCHANGE WITH A LIGAND IN HEXACARBONYLDI-IRON COMPOUNDS [(MU-RS)2FE2(CO)6] [J].

DARCHEN, A ;

MOUSSER, H ;

PATIN, H .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (14) :968-970

[9] FTIR characterization of the active site of the Fe-hydrogenase from Desulfovibrio desulfuricans [J].

De Lacey, AL ;

Stadler, C ;

Cavazza, C ;

Hatchikian, EC ;

Fernandez, VM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (45) :11232-11233

[10] A MOSSBAUER SPECTROSCOPIC INVESTIGATION OF THE IRON SULFIDO-CARBONYL CLUSTERS [FE2(MU-2-S)2(CO)6], [FE3(MU-3-S)2(CO)9] AND THE 1-1 ADDUCT [FE2(MU-2-S)2(CO)6].[FE3(MU-3-S)2(CO)9] [J].

DILWORTH, JR ;

MORTON, S ;

OCONNOR, M ;

SILVER, J .

INORGANICA CHIMICA ACTA, 1987, 127 (01) :91-94

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