Department of Molecular Chemistry and Biochemistry, Doshisha University, Tatara Miyakotani 1-3, Kyotanabe, Kyoto 610-0321, Japan.
J Am Chem Soc. 2012 Aug 15;134(32):13236-9. doi: 10.1021/ja306089q. Epub 2012 Aug 1.
The conversion of peroxodiiron(III) to high-spin S = 2 oxodiiron(IV) via reversible O-O 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, Mössbauer, and resonance Raman spectroscopy to gain insight into the O(2) 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-O bond scission.
具有双-tpa 双齿配体 6-hpa 的二铁配合物中，通过可逆 O-O 键断裂将过氧二铁(III)转化为高自旋 S = 2 氧二铁(IV)，已通过元素分析、烯烃环氧化的动力学测量、冷喷雾电离质谱以及电子吸收、穆斯堡尔和共振拉曼光谱进行了表征，以深入了解可溶性甲烷单加氧酶的 O(2) 活化机制。这是首例高效氧化烯烃为环氧化物的高自旋 S = 2 氧二铁(IV)物种的合成实例。过氧二铁(III)和高自旋 S = 2 氧二铁(IV)部分的双稳定性是可逆 O-O 键断裂的关键特征。
