Dioxygen Reactivity of an Iron Complex of 2-Aminophenol-Appended Ligand: Crystallographic Evidence of the Aromatic Ring Cleavage Product of the 2-Aminophenol Unit

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• 作者：Ganesh Chandra Paul ; Sridhar Banerjee ; Chandan Mukherjee
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：January 17, 2017
• 年：2017
• 卷：56
• 期：2
• 页码：729-736
• 全文大小：483K
• ISSN：1520-510X

文摘

2-Aminophenol appended pentadentate ligand H₂Gan^AP was synthesized by mixing equimolar amounts of 2-[bis(2-pyridylmethyl)aminomethyl]aniline (A) and 3,5-di-tert-butyl catechol in hexane in the presence of Et₃N under air. The ligand reacted with Fe(ClO₄)₂·6H₂O or Fe(ClO₄)₃·6H₂O in the presence of tetrabutylammonium perchlorate, and Et₃N under air and provided a μ₂ oxo-bridged dinuclear iron complex (1). X-ray single-crystal analysis of complex 1 revealed the presence of a furan derivative, resulting from the oxidative aromatic C–C bond cleavage product of 2-aminophenol derivative, in the coordination sphere of each iron center. Mechanistic investigation for the formation of complex 1 established that in the absence of molecular oxygen no oxidation of the appended 2-amidophenolate unit took place. An iron(III)–amidophenolate complex, formed initially, further reacted with molecular oxygen and caused oxidative aromatic C–C bond cleavage via a putative alkylperoxo species.