Solution and structural characterization of iron(II) complexes with ortho-halogenated phenolates: insights into potential substrate binding modes in hydroquinone dioxygenases.
Solution and structural characterization of iron(II) complexes with ortho-halogenated phenolates: insights into potential substrate binding modes in hydroquinone dioxygenases.
复制标题
铁 (II) 与邻卤化酚盐复合物的溶液和结构表征：深入了解氢醌双加氧酶中潜在的底物结合模式。
DOI：
10.1021/ic101377u
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发表时间：
2010
影响因子：
4.6
通讯作者：
Patrick L. Holland
中科院分区：
文献类型：
--
作者：
Sara S. Rocks;W. Brennessel;T. Machonkin;Patrick L. Holland
新配体cis-1，3，5-tris-(E)-(tolylideneimino)cyclohexane(tach-o-tolyl)与Fe(II)形成1：1的络合物。取代酚类化合物的加入形成了1：1：1的配体：铁：酚类络合物，对其进行了固相和溶液的表征。只有当酚类上有邻位卤素时，酚类才能与络合物完全结合。含有邻位卤代苯酚的三元络合物具有较短的Fe-卤素距离，而含有非配位但大小相似的邻甲基酚的络合物具有显著不同的构象和配位几何构型。因此，很可能是金属-卤素相互作用稳定了络合物。这些络合物中的铁(II)-卤素相互作用可能解释了PCPA和LINE的底物专一性，这两种酶优先结合邻位上含有卤素取代基的酚和对苯二酚。
The new ligand cis,cis-1,3,5-tris-(E)-(tolylideneimino)cyclohexane (TACH-o-tolyl) forms a 1:1 complex with iron(II). Addition of substituted phenolates forms 1:1:1 ligand:iron:phenolate complexes, which have been characterized both in the solid state and in solution. There is complete binding of the phenolate to the complex only when there are ortho-halogens on the phenolate. The tertiary complexes with ortho-halo-substituted phenolates exhibit short Fe-halogen distances, and the complex containing a non-coordinating but similarly sized ortho-methyl phenolate has a significantly different conformation and coordination geometry. Therefore, it is likely that the metal-halogen interaction stabilizes the complexes. The iron(II)-halogen interaction in these complexes may explain the substrate specificity of PcpA and LinE, enzymes that preferentially bind phenols and hydroquinones containing halogen substituents in ortho positions.