Resonance Raman and Electrocatalytic Behavior of Thiolate and Imidazole Bound Iron Porphyrin Complexes on Self Assembled Monolayers: Functional Modeling of Cytochrome P450

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• 作者：Kushal Sengupta ; Sudipta Chatterjee ; Subhra Samanta ; Sabyasachi Bandyopadhyay ; Abhishek Dey
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 18, 2013
• 年：2013
• 卷：52
• 期：4
• 页码：2000-2014
• 全文大小：858K
• 年卷期：v.52,no.4(February 18, 2013)
• ISSN：1520-510X

文摘

Electrodes bearing thiolate and imidazole coordinated iron porphyrin catalysts are constructed and characterized using resonance Raman spectroscopy, absorption spectroscopy, and electrochemistry. The cyclic voltammetry data and their pH dependences are used to establish the nature of the exchangeable trans ligands in both of these cases. In situ monitoring of partially reduced oxygen species (PROS) produced during O₂ reduction using rotating ring disc electrochemistry (RRDE) experiments provide direct insight into the 鈥減ush-effect鈥?of the thiolate ligand. The thiolate bound iron porphyrin electrode generates highly oxidizing species on the electrode during electrocatalytic O₂ reductions which are very reactive. These surfaces can utilize these oxidants to catalytically hydroxylate strong C鈥揌 bonds using molecular O₂ with turnover numbers as high as 200.