Reversible O鈥揙 Bond Scission of Peroxodiiron(III) to High-Spin Oxodiiron(IV) in Dioxygen Activation of a Diiron Center with a Bis-tpa Dinucleating Ligand as a Soluble Methane Monooxygenase Model

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• 作者：Masahito Kodera ; Yuka Kawahara ; Yutaka Hitomi ; Takashi Nomura ; Takashi Ogura ; Yoshio Kobayashi
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：August 15, 2012
• 年：2012
• 卷：134
• 期：32
• 页码：13236-13239
• 全文大小：236K
• 年卷期：v.134,no.32(August 15, 2012)
• ISSN：1520-5126

文摘

The conversion of peroxodiiron(III) to high-spin S = 2 oxodiiron(IV) via reversible O鈥揙 bond scission in a diiron complex with a bis-tpa dinucleating ligand, 6-hpa, has been characterized by elemental analysis; kinetic measurements for alkene epoxidation; cold-spray ionization mass spectrometry; and electronic absorption, M枚ssbauer, and resonance Raman spectroscopy to gain insight into the O₂ activation mechanism of soluble methane monooxygenases. This is the first synthetic example of a high-spin S = 2 oxodiiron(IV) species that oxidizes alkenes to epoxides efficiently. The bistability of the peroxodiiron(III) and high-spin S = 2 oxodiiron(IV) moieties is the key feature for the reversible O鈥揙 bond scission.