Department of Inorganic Chemistry, Indian Association for the Cultivation of Science (IACS), 2A and 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Inorg Chem. 2010 May 17;49(10):4518-23. doi: 10.1021/ic902462k.
The synthesis and characterization of an iron-catecholate model complex of a tridentate 2-N-1-carboxylate ligand derived from L-proline are reported. The X-ray crystal structure of the complex [(L)(3)Fe(3)(DBC)(3)] (1) (where L is 1-(2-pyridylmethyl)pyrrolidine-2-carboxylate and DBC is the dianion of 3,5-di-tert-butyl catechol) reveals that the tridentate ligand binds to the iron center in a facial manner and mimics the 2-his-1-carboxylate facial triad motif observed in extradiol-cleaving catechol dioxygenases. The iron(III)-catecholate complex (1) reacts with dioxygen in acetonitrile in ambient conditions to cleave the C-C bond of catecholate. In the reaction, an equal amount of extra- and intradiol cleavage products are formed without any auto-oxidation product. The iron-catecholate complex is a potential functional model of extradiol-cleaving catechol dioxygenases.
报告了一种铁-儿茶酚配合物模型的合成与表征，该模型配合物由 L-脯氨酸衍生的三齿 2-N-1-羧酸配体得到。配合物[(L)3Fe3(DBC)3]（1）（其中 L 是 1-(2-吡啶甲基)吡咯烷-2-羧酸，DBC 是 3,5-二叔丁基儿茶酚的二阴离子）的 X 射线晶体结构表明，三齿配体以面式方式与铁中心结合，并模拟了外二醇切割儿茶酚双加氧酶中观察到的 2-组氨酸-1-羧基面对面三联体基序。铁(III)-儿茶酚配合物（1）在环境条件下与乙腈中的氧气反应，切割儿茶酚的 C-C 键。在反应中，形成了等量的外二醇和内二醇裂解产物，没有任何自氧化产物。该铁-儿茶酚配合物是外二醇切割儿茶酚双加氧酶的潜在功能模型。
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