Investigation of amino acid containing [FeFe] hydrogenase models concerning pendant base effects.
The present investigations deal with the modeling of the peptide surrounding of [FeFe] hydrogenase using amine containing disulphides to simulate possible influences of the amino acid lysine (K237) on the electrochemical and electrocatalytic properties of biomimetic compounds based on [Fe2S2] moieties. Fe(3)(CO)(12) was reacted with Boc-4-amino-1,2-dithiolane, Boc-Adt-OMe (Adt=4-amino-1,2-dithiolane-4-carboxylic acid, Boc=tert-butoxycarbonyl) and Boc-Adp tert-butyl ester (Adp=(S)-2-amino-3-(1,2-dithiolan-4-yl)propionic acid) to elongate the Fecdots, three dots, centeredN distance in comparison to the well known [Fe(2){(SCH(2))(2)NR}(CO)(6)] model complexes. Efforts to deprotect the complexes containing Boc-4-amino-1,2-dithiolane with trifluoroacetic acid result in the formation of [Fe(3)(mu(3)-O)(mu-O(2)C(2)F(3))(6)(OC(4)H(8))(2)(H(2)O)]. The novel [2Fe2S] complexes are characterized using spectroscopic, electrochemical techniques and X-ray diffraction studies.
Apfel
Ulf-Peter
UP
Institute for Inorganic and Analytical Chemistry, Friedrich-Schiller University Jena, Germany.
Kowol
Christian R
CR
Halpin
Yvonne
Y
Kloss
Florian
F
Kübel
Joachim
J
Görls
Helmar
H
Vos
Johannes G
JG
Keppler
Bernhard K
BK
Morera
Enrico
E
Lucente
Gino
G
Weigand
Wolfgang
W
D055162:Biocatalysis; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D018716:Molecular Mimicry; D015394:Molecular Structure; D017550:Spectroscopy, Fourier Transform Infrared
D007506:Iron-Sulfur Proteins; D008024:Ligands; C118830:iron hydrogenase; D006864:Hydrogenase