Spectroscopic and crystallographic evidence for the N-protonated FeIFeI azadithiolate complex related to the active site of Fe-only hydrogenases.
نویسندگان
چکیده
The complex [{(mu-SCH2)2N(CH2C6H4-2-Br)}Fe2(CO)6] and its N-protonated species, as structural models of the Fe-only hydrogenase active site, were identified spectroscopically and crystallographically, and their molecular structures show the 0.04-0.1 A lengthening of the three N-C bonds and an intramolecular HBr contact (2.82 Angstroms) in the crystalline state of the N-protonated species.
منابع مشابه
An insight into the protonation property of a diiron azadithiolate complex pertinent to the active site of Fe-only hydrogenases.
Protonation of [{(mu-SCH2)2N(C6H4-p-NO2)}{Fe(CO)2(PMe3)}2] in the presence of 4 equiv. of HOTf afforded two species, a micro-hydride diiron complex, the molecular structure of which was crystallographically characterized, and a micro-S-protonated species, which was readily deprotonated in the presence of pyridine.
متن کاملProtonation, electrochemical properties and molecular structures of halogen-functionalized diiron azadithiolate complexes related to the active site of iron-only hydrogenases.
Diiron complexes [{(micro-SCH2)2NCH2C6H4X}{Fe(CO)2L}2] (L = CO, X = 2-Br, 1; 2-F, 2; 3-Br, 3; L = PMe(3), X = 2-Br, 4) were prepared as biomimetic models of the iron-only hydrogenase active site. The N-protonated species [(NH)]+ClO(4)(-), [(NH)](+)ClO(4)(-) and the micro-hydride diiron complex [4(FeHFe)]+PF(6)(-) were obtained in the presence of proton acids and well characterized. The protonat...
متن کاملFluorophenyl-substituted Fe-only hydrogenases active site ADT models: different electrocatalytic process for proton reduction in HOAc and HBF4/Et2O.
A set of fluorophenyl-substituted adt-bridged Fe2S2 active site models of Fe-only hydrogenase, [(micro-SCH2)2NR]Fe2(CO)6 (, R=C6F4CF3-p; , R=C6H4CF3-p) and [(micro-SCH2)2NR]Fe2(CO)5(PPh3) (, R=C6F4CF3-p; , R=C6H4CF3-p), have been synthesized and well characterized. Spectroscopic and electrochemical studies demonstrate that the aryl-substituted complexes are stable toward a strong acid HBF4/Et2O...
متن کاملIron carbonyl sulfides, formaldehyde, and amines condense to give the proposed azadithiolate cofactor of the Fe-only hydrogenases.
The azadithiolate (SCH2NHCH2S) cofactor proposed to occur in the Fe-only hydrogenases forms efficiently by the condensation of Fe2(SH)2(CO)6 (1), formaldehyde, and ammonia (as (NH4)2CO3). The resulting Fe2[(SCH2)2NH](CO)6 reacts with Et4NCN to give (Et4N)2[Fe2[(SCH2)2NH](CO)4(CN)2], for which crystallographic characterization confirmed an axial N-H and an elongated C-S bond of 1.858(3) A. Prima...
متن کاملX-ray crystallographic and EPR spectroscopic analysis of HydG, a maturase in [FeFe]-hydrogenase H-cluster assembly.
Hydrogenases use complex metal cofactors to catalyze the reversible formation of hydrogen. In [FeFe]-hydrogenases, the H-cluster cofactor includes a diiron subcluster containing azadithiolate, three CO, and two CN(-) ligands. During the assembly of the H cluster, the radical S-adenosyl methionine (SAM) enzyme HydG lyses the substrate tyrosine to yield the diatomic ligands. These diatomic produc...
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عنوان ژورنال:
- Chemical communications
دوره 25 شماره
صفحات -
تاریخ انتشار 2005