کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1327423 | 977481 | 2006 | 8 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Tris(N-pyrrolidinyl)phosphine substituted diiron dithiolate related to iron-only hydrogenase active site: Synthesis, characterization and electrochemical properties Tris(N-pyrrolidinyl)phosphine substituted diiron dithiolate related to iron-only hydrogenase active site: Synthesis, characterization and electrochemical properties](/preview/png/1327423.png)
A tris(N-pyrrolidinyl)phosphine (P(NC4H8)3) monosubstituted complex, [(μ-pdt)Fe2(CO)5P(NC4H8)3] (2) was synthesized as a functional model of the hydrogen-producing capability of the iron hydrogenase active site. The structure was fully characterized by X-ray crystallography. IR and electrochemical studies have indicated that the P(NC4H8)3 ligand has better electron-donating ability than that of those phosphine ligands, such as PMe3, PTA (1,3,5-triaza-7-phosphaadamantane), PMe2Ph PPh3, and P(OEt)3. The electrocatalytic activity of 2 was recorded in CH3CN in the absence and presence of weak acid, HOAc. The cathodic shift of potential at −1.98 V and the dependence of current on acid concentration have indicated that complex 2 can catalyze the reduction of protons to hydrogen at its Fe0FeI level in the presence of HOAc. IR spectroelectrochemical experiments are conducted during the reduction of 2 under nitrogen and carbon monoxide, respectively. The formation of a bridging CO group during the reduction of 2 at −1.98 V has been identified using IR spectroelectrochemical techniques, and an electrocatalytic mechanism of 2 consistent with the spectroscopic and electrochemical results is proposed.
A tris(N-pyrrolidinyl)phosphine monosubstituted complex, [(μ-pdt)Fe2(CO)5P(NC4H8)3] was synthesized as a functional model of the hydrogen-producing capability of the iron hydrogenase active site.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 691, Issue 22, 1 November 2006, Pages 4633–4640