N₂S₂ chelating agents as Cys-X-Cys biomimics for Fe(NO) and Fe(NO)₂ complexes /

Bibliographic Details
Main Author: Chiang, Chao-Yi, 1969-
Other Authors: Darensbourg, Marcetta Y. (Thesis advisor)
Format: Thesis eBook
Language:English
Published: [College Station, Tex.] : [Texas A&M University], [2006]
Subjects:
Online Access:Link to OAK Trust copy
Description
Abstract:Nitric oxide plays an important role in many biological functions. A metallo derivative in biological systems is a protein-bound dinitrosyl iron complex (DNIC), which results from iron-sulfur cluster degradation in the presence of excess NO. Through model complexes I have examined the fundamental properties of a dithiolato-Fe(NO)₂ complex, bismercaptoethandiazacyclooctane iron dinitrosyl or (H⁺bme-daco)Fe(NO)₂ as a biomimic of dicysteinate coordination of [Fe(NO)₂]. This complex was prepared and fully characterized in my studies. The DNIC moiety is in its oxidized state, {Fe(NO)₂}⁹. Through reaction studies, monitored by IR spectroscopy (H⁺N₂S₂)Fe(NO)₂ (N₂S₂ = bme-dach. Bme-pda) has been shown to transfer NO to Fe[superscript]III in (TPP)FeCl (TPP = meso-tetraphenylporphyrin) as NO⁻. The remaining mononitrosyl converts into complex (N₂S₂)Fe(NO). The (N₂S₂)Fe(NO) complexes (N₂S₂ = bme-daco, bme*-daco, bme-dach) were prepared by direct reaction of dimeric [(N₂S₂)Fe]₂ and NO gas. The analogous (N₂S₂)Co(NO) complex (N₂S₂ = bme-dach) has also been prepared. The series of square pyramidal (N₂S₂)M(NO) have been studied by cyclic voltammetry and v(NO) IR spectroscopy.
Item Description:"Major Subject: Chemistry"
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