Abstract
The compound (Et(4)N)(2)[Fe(4)S(4)(SCH(2)Ph)(4)] has been prepared and its structure determined by x-ray diffraction. The Fe(4)S(4) core of the anion possesses a configuration of D(2d) symmetry that is closely related to the Fe(4)S(4) active-site structures of the high-potential iron protein from Chromatium and the ferredoxin from Micrococcus aerogenes. Electronic properties of the tetrameric anion have been partially characterized by measurement of proton magnetic resonance, Mössbauer, photoelectron, and electronic spectra, and magnetic susceptibility. Comparison of corresponding properties of [Fe(4)S(4)(SCH(2)Ph)(4)](2-) and the proteins implies that the oxidation levels of the synthetic tetramer, the reduced form of the high-potential protein, and the oxidized form of the 8-Fe ferredoxins are equivalent. The tetramer possesses the one-electron redox capacity associated with the 4-Fe centers of the ferredoxins. The structural and collective electronic features of [Fe(4)S(4)(SCH(2)Ph)(4)](2-) reveal it to be the first well-defined synthetic analogue of the active site of an iron-sulfur protein.
MeSH Terms
Bacterial Proteins
Chemical Phenomena
Chemistry, Physical
Ferredoxins
Iron
Iron Isotopes
Magnetic Resonance Spectroscopy
Magnetics
Models, Chemical
Organometallic Compounds
Oxidation-Reduction
Potentiometry
Spectrum Analysis
Sulfides
Temperature
X-Ray Diffraction
Chemicals
Bacterial Proteins
Ferredoxins
Iron Isotopes
Organometallic Compounds
Sulfides
Iron
Authors & Affiliations
6 authors, click to expand affiliations / ORCID
Herskovitz T
Averill B A
Holm R H
Ibers J A
Phillips W D
Weiher J F
References (19)
19 references, click to expand
-
Chemical characterization of high potential iron proteins from Chromatium and Rhodopseudomonas gelatinosa.
Biochim Biophys Acta. 1967 Jun 27;140(2):291-311
PMID: 6048308
-
Structure of rubredoxin: an x-ray study to 2.5 A resolution.
J Mol Biol. 1970 Jun 14;50(2):391-406
PMID: 5476919
-
Mössbauer spectroscopy of non-heme iron proteins.
Biochemistry. 1968 Apr;7(4):1591-6
PMID: 5677846
-
On the structure of the iron-sulfur complex in the two-iron ferredoxins.
Biochim Biophys Acta. 1971 Dec 7;253(2):373-84
PMID: 4332306
-
Iron-mercaptoethanol-inorganic sulfide complex. Possible model for the chromophore of nonheme iron proteins.
Biochemistry. 1970 May 12;9(10):2127-33
PMID: 4315131
-
PMR and magnetic susceptibility studies on Clostridium acidi-urici ferredoxin.
Biochem Biophys Res Commun. 1971 Feb 19;42(4):705-13
PMID: 5543952
-
Polarographic activity and electrolytic reduction of ferredoxin.
FEBS Lett. 1971 Oct 1;17(2):241-244
PMID: 11946037
-
Ferredoxins: chemistry and function in photosynthesis, nitrogen fixation, and fermentative metabolism.
Adv Enzymol Relat Areas Mol Biol. 1970;33:119-76
PMID: 4393906
-
Structure of the iron-sulfur cluster in the Chromatius iron protein at 2.25 Angstrom resolution.
Cold Spring Harb Symp Quant Biol. 1972;36:381-5
PMID: 4508152
-
Proton magnetic resonance studies of Chromatium high-potential iron protein.
Proc Natl Acad Sci U S A. 1970 Oct;67(2):682-7
PMID: 5289015
-
THE NATURE OF IRON IN FERREDOXIN.
Proc Natl Acad Sci U S A. 1964 Jun;51:1085-92
PMID: 14215629
-
[pH-dependent magnetic and spectral properties of oxidized ferredoxin from Clostridium pasteurianum].
Eur J Biochem. 1967 Sep;2(2):176-81
PMID: 6078530
-
Hyperfine structure of (57Fe) iron in the Mössbauer spectrum of the high-potential iron protein from Chromatium.
Biochem J. 1970 Sep;119(2):289-91
PMID: 5488916
-
Structure of the Fe-S complex in a bacterial ferredoxin.
Nature. 1972 Jan 7;235(5332):40-2
PMID: 4550392
-
Proton magnetic resonance study of ferredoxin from Clostridium pasteurianum.
Proc Natl Acad Sci U S A. 1970 Apr;65(4):797-804
PMID: 5266908
-
Iron-sulfide chelates of some sulfur-containing peptides as model complex of non-heme iron proteins.
Biochem Biophys Res Commun. 1972 Jan 31;46(2):335-40
PMID: 5057878
-
The magnetic susceptibility of oxidized and reduced ferredoxins from spinach and parsley and the high potential protein from Chromatium.
J Biol Chem. 1969 May 10;244(9):2275-7
PMID: 5783833
-
The structure of a non-heme iron protein: rubredoxin at 1.5 Angstrom resolution.
Cold Spring Harb Symp Quant Biol. 1972;36:359-67
PMID: 4508149
-
Molar extinction coefficient and iron and sulfide content of clostridial ferredoxin.
J Biol Chem. 1970 Oct 10;245(19):4982-7
PMID: 5506267