Mechanistic Study for the Facile Oxidation of Trimethoprim on a Manganese Porphyrin Incorporated Glassy Carbon Electrode

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• 作者：Leena Rajith ; A. K. Jissy ; Krishnapillai Girish Kumar ; Ayan Datta
• 刊名：Journal of Physical Chemistry C
• 出版年：2011
• 出版时间：November 10, 2011
• 年：2011
• 卷：115
• 期：44
• 页码：21858-21864
• 全文大小：903K
• 年卷期：v.115,no.44(November 10, 2011)
• ISSN：1932-7455

文摘

The electrocatalysis of [5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]Mn(III)chloride (TMOPPMn(III)Cl) toward the oxidation of trimethoprim was investigated by electrochemical and computational methods. Voltammetric analysis demonstrates the ability of TMOPPMn(III)Cl to act as an electrocatalyst for the oxidation of trimethoprim. DFT calculations were performed at the B3LYP level to detect the site of oxidation as well as to survey the role of manganese porphyrin in the facile oxidation of trimethoprim. Quantum chemical calculations affirm that the deprotonation of NH₂ attached to C4 is more energetically favorable as compared to deprotonation of the C2 amino group. Also, the deprotonation of trimethoprim in the TMOPPMn(III)Cl-catalyzed reaction results in the formation of a more stable anion as compared to the uncatalyzed reaction. Atoms in molecule (AIM) analysis and natural bond orbital (NBO) analysis also substantiate the utility of TMOPPMn(III)Cl in trimethoprim oxidation by confirming the coordination of trimethoprim to manganese porphyrin on removal of proton.