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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Iron(III) complexes with meridional ligands as functional models of intradiol-cleaving catechol dioxygenases
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Iron(III) complexes with meridional ligands as functional models of intradiol-cleaving catechol dioxygenases

机译：具有子午线配体的铁（III）络合物作为二醇内切割儿茶酚双加氧酶的功能模型

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摘要

Six dichloroiron(III) complexes of 1,3-bis(2′-arylimino)isoindoline (BAIH) with various N-donor aryl groups have been characterized by spectroscopy (infrared, UV-vis), electrochemistry (cyclic voltammetry), microanalysis, and in two cases X-ray crystallography. The structurally characterized Fe ~(III)Cl_2(L~n) complexes (n = 3, L~3 = 1,3-bis(2′-thiazolylimino)isoindoline and n = 5, L~5 = 1,3-bis(4-methyl-2′-piridylimino)isoindoline) are five-coordinate, trigonal bipyramidal with the isoindoline ligands occupying the two axial and one equatorial positions meridionally. These compounds served as precursors for catechol dioxygenase models that were formed in solution upon addition of 3,5-di-tert-butylcatechol (H_2DBC) and excess triethylamine. These adducts react with dioxygen in N,N-dimethylformamide, and the analysis of the products by chromatography and mass spectrometry showed high intradiol over extradiol selectivity (the intradiol/extradiol product ratios varied between 46.5 and 6.5). Kinetic measurements were performed by following the change in the intensity of the catecholate to iron ligand-to-metal charge transfer (LMCT) band, the energy of which is influenced by the isoindolinate-ligand (827-960 nm). In combination with electrochemical investigations the kinetic studies revealed an inverse trend between reaction rates and oxidation potentials associated with the coordinated DBC~(2-). On the basis of these results, a substrate activation mechanism is suggested for this system in which the geometry of the peroxide-bridged intermediate may be of key importance in regioselectivity.
机译：1,3-双（2'-芳基）异吲哚啉（BAIH）与各种N-给体芳基的六种二氯铁（III）配合物已通过光谱（红外，紫外可见），电化学（循环伏安），微量分析，以及两种情况下的X射线晶体学分析。 Fe〜（III）Cl_2（L〜n）配合物的结构特征（n = 3，L〜3 = 1,3-bis（2'-thiazolylimino）isoindoline and n = 5，L〜5 = 1,3-bis （4-甲基-2'-哌啶基氨基）异吲哚啉是五配位的三角双锥体，异吲哚啉配体在子午线上占据两个轴向和一个赤道位置。这些化合物用作儿茶酚双加氧酶模型的前体，该模型是在添加3,5-二叔丁基儿茶酚（H_2DBC）和过量的三乙胺后在溶液中形成的。这些加合物与N，N-二甲基甲酰胺中的双氧反应，并且通过色谱和质谱分析产物，显示出较高的内二醇相对于额外的二醇选择性（内二醇/雌二醇的产物比率在46.5至6.5之间变化）。通过跟踪儿茶酚酸至铁配体-金属电荷转移（LMCT）谱带的强度变化来进行动力学测量，其能量受异吲哚酸酯-配体（827-960 nm）影响。与电化学研究相结合，动力学研究揭示了与配位DBC〜（2-）相关的反应速率和氧化电位之间的反趋势。基于这些结果，提出了针对该系统的底物活化机制，其中过氧化物桥接的中间体的几何形状可能对区域选择性至关重要。

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