An insight into the protonation property of a diiron azadithiolate complex pertinent to the active site of Fe-only hydrogenases.
نویسندگان
چکیده
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.
منابع مشابه
Protonation, 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 کاملArtificially maturated [FeFe] hydrogenase from Chlamydomonas reinhardtii: a HYSCORE and ENDOR study of a non-natural H-cluster.
Hydrogenases are enzymes that catalyze the oxidation of H2 as well as the reduction of protons to form H2. The active site of [FeFe] hydrogenase is referred to as the "H-cluster" and consists of a "classical" [4Fe-4S] cluster connected via a bridging cysteine thiol group to a unique [2Fe]H sub-cluster, containing CN(-) and CO ligands as well as a bidentate azadithiolate ligand. It has been rece...
متن کاملSpectroscopic and crystallographic evidence for the N-protonated FeIFeI azadithiolate complex related to the active site of Fe-only hydrogenases.
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.
متن کاملStructures, protonation, and electrochemical properties of diiron dithiolate complexes containing pyridyl-phosphine ligands.
Diiron complexes containing pyridyl-phosphine ligands, that is, (mu-pdt)[Fe(2)(CO)(5)L] (pdt = S(CH(2))(3)S, L = Ph(2)PCH(2)Py, Ph(2)PPy, ) and (micro-pdt)[Fe(CO)(2)(PMe(3))][Fe(CO)(2)L] (L = Ph(2)PCH(2)Py, Ph(2)PPy, ) were prepared as model complexes of the [FeFe]-hydrogenase active site. Protonation of and by HOTf afforded the pyridyl-nitrogen protonated products [H(N)][OTf] and [H(N)][OTf], ...
متن کاملNew class of diiron dithiolates related to the Fe-only hydrogenase active site: synthesis and characterization of [Fe2(SR)(2)(CNMe)7]2+.
Electron-rich polyisocyano derivatives Fe(2)(S(2)C(n)H(2n)(CO)(6-x)(CNMe)(x) (x approximately 4) undergo oxidatively induced (FeCp(2)(+)) reaction with additional CNMe to give [Fe(2)(SR)(2)(CNMe)(7)](PF(6))(2), a new class of iron thiolates. Crystallographic characterization established that the 34 e(-) dinuclear core resembles the oxidized (H(2)-binding) form of the active sites of the Fe-only...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 3 شماره
صفحات -
تاریخ انتشار 2006