Regioselective arene hydroxylation mediated by a (mu-peroxo)diiron(III) complex: a functional model for toluene monooxygenase.
Regioselective arene hydroxylation mediated by a (mu-peroxo)diiron(III) complex: a functional model for toluene monooxygenase.
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DOI：
10.1021/ja063987z
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发表时间：
2007-01
影响因子：
15
通讯作者：
Mai Yamashita;H. Furutachi;T. Tosha;S. Fujinami;Wataru Saito;Y. Maeda;Kenji Takahashi;Koji Tanaka-Koji-T
中科院分区：
文献类型：
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作者：
Mai Yamashita;H. Furutachi;T. Tosha;S. Fujinami;Wataru Saito;Y. Maeda;Kenji Takahashi;Koji Tanaka-Koji-T
二铁(II)配合物[Fe2(LPh_4)(RCO_2)]~(2+)(R=Ph_3或Ph)与氧气反应生成过氧二铁(III)配合物[Fe_2(LPh_4)(RCO_2)(O_2)]~(2+)。它们的反应性可以很大程度上由桥联羧酸盐的立体化学来控制。与Ph3CCO2的过氧络合物的热分解导致支撑配体的苯基之一发生区域选择性羟基化，模拟甲苯单加氧酶羟基酶的活性，而与PhCO2的过氧络合物表现出可逆的脱氧作用。
Diiron(II) complexes, [Fe2(LPh4)(RCO2)]2+ (R = Ph3C or Ph), react with dioxygen to generate peroxodiiron(III) complexes [Fe2(LPh4)(RCO2)(O2)]2+. Their reactivities can be greatly controlled by the stereochemistry of the bridging carboxylates. Thermal decomposition of a peroxo complex with Ph3CCO2 resulted in regioselective hydroxylation of one of phenyl groups of the supporting ligand, which mimics toluene monooxygenase hydroxylase activity, whereas a peroxo complex with PhCO2 exhibited reversible deoxygenation.