Homo-and heterodinuclear complexes of the tris(catecholamide)derivative of a tetraazamacrocycle with Fe~(3+),Cu~(2+)and Zn~(2+)metal ions

Krassimira P.Guerra; Rita Delgado

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Homo-and heterodinuclear complexes of the tris(catecholamide)derivative of a tetraazamacrocycle with Fe~(3+),Cu~(2+)and Zn~(2+)metal ions

机译：四氮杂cro环的三（邻苯二甲酰胺）衍生物的均和杂异核配合物与Fe〜（3 +），Cu〜（2+）和Zn〜（2+）金属离子

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The new ditopic catecholamide 3,7,11-tris-{N-[3,4-(dihydroxybenzoyl)-aminopropyr]}derivative of a 14-membered tetraazamacrocycle containing pyridine(H6L1)has been synthesized.The protonation constants of(L1)~(6-)and the stability constants of its mono-,homo-and hetero-dinuclear complexes with Fe~(3+),Cu~(2+)and Zn~(2+)metal ions were determined at 298.2 K and ionic strength 0.10 mol dm~(-3)in KNO3.The large overall basicity of the ligand was ascribed to the very high protonation constants of the catecholate groups,and its acid-base behaviour was correlated with the presence of tertiary nitrogen atoms and secondary amide functions.The UV-vis spectrum of the red solution of[FeL1]~(3-)complex exhibits the LMCT band of catecholate to iron(III),and its EPR spectrum revealed a typical isotropic signal of a rhombic distorted ferric centre in a high-spin state and E/D approx=0.31,both characteristic of a tris-catecholate octahedral environment.The ligand forms with copper(II)and zinc(II)ions mono-and dinuclear protonated complexes and their stability constants were determined,except for the[ML1]~(4-)complexes as the last proton is released at very high pH.Electronic spectroscopic studies of the copper complexes revealed the involvement of catecholate groups in the coordination to the metal centre in the mono-and dinuclear copper(II)complexes.This information together with the determined stability constants indicated that the copper(II)ion can be involved in both types of coordination site of the ligand with comparable binding affinity.The EPR spectrum of[Cu2L1]~(2-)showed a well resolved seven-line hyperfme pattern of copper(II)dinuclear species typical of a paramagnetic triplet spin state with weak coupling between the two metal centres.Thermodynamically stable heterodinuclear complexes,[CuFeH_hL1]~(h-1)(h=0-3)and[CuZnH_hL1]~(h-2)(h=0-4),were formed as expected from a ditopic ligand having two dissimilar coordination sites.At physiological pH,the[CuFeL1]~-complex is formed at approx=100%.The formation of the[CuFeH_hL1]~(h-1)complexes in solution was supported by electronic spectroscopic measurements.The data indicated the specific coordination of each metal centre at the dissimilar sites of the ligand,the iron(III)bound to the oxygen donors of the catecholate arms and the copper(II)coordinated to the amine donors of the macrocyclic ring.The two metal centres are weakly coupled,due to the fairly large distance between them.

机译：合成了含吡啶（H6L1）的14元四氮杂大环的新的对位儿茶酚酰胺3,7,11-三-{N- [3,4-（二羟基苯甲酰基）-氨基丙基]}衍生物。（L1）的质子化常数测定了〜（6-）及其与Fe〜（3 +），Cu〜（2+）和Zn〜（2+）金属离子的单，均和异核配合物的稳定性常数。离子强度为0.10 mol dm〜（-3）在KNO3中。配体的整体碱度较高是由于儿茶酚基团的质子化常数很高，其酸碱行为与叔氮原子和仲氮原子的存在有关。 [FeL1]〜（3-）配合物红色溶液的UV-vis光谱显示儿茶酚酸对铁（III）的LMCT谱带，其EPR谱图揭示了菱形畸变的铁中心的典型各向同性信号。具有三旋邻苯二酚八面体环境的高自旋态和E / D约= 0.31。配体与铜（II）和锌（II）离子形成除了在高pH条件下释放最后一个质子的[ML1]〜（4-）配合物外，还测定了正，双核质子配合物及其稳定性常数。电子光谱研究表明，铜配合物参与了儿茶酚酸基团的形成。该信息与确定的稳定常数一起表明，铜（II）离子可以以可比的结合亲和力参与配体的两种类型的配位位点。[Cu2L1]〜（2-）的EPR谱显示了良好分辨的铜（II）双核物种的七线超清晰图谱，典型为顺磁性三重态自旋态，两个金属中心之间的耦合较弱。热力学稳定的异双核配合物[CuFeH_hL1]〜（h-1）（h = 0-3）和[CuZnH_hL1]〜（h-2）（h = 0-4）如预期般由具有两个不同配位点的对位配体形成。在pH下，形成[CuFeL1]〜络合物大约100％时，溶液中[CuFeH_hL1]〜（h-1）络合物的形成得到电子光谱的支持。数据表明每个金属中心在配体，铁（ III）与邻苯二酚臂的氧供体结合，与大环环的胺供体配位的铜（II）。由于两个金属中心之间的距离较大，它们之间的耦合较弱。

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《Dalton transactions: An international journal of inorganic chemistry》 |2008年第4期|共12页
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Krassimira P.Guerra; Rita Delgado;
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机译：四氮杂cro环的三（邻苯二甲酰胺）衍生物的均和杂异核配合物与Fe〜（3 +），Cu〜（2+）和Zn〜（2+）金属离子
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机译：将每种金属离子的合成浸出溶液分离有两种组分（Mn 2 + / sop>，Cu 2 + ），（Mn 2 + / sup>，fe 2 + ），（Fe 3 + ，cu 2 + ），（ni 2 + ，CO ^{2 + ）}

Homo-and heterodinuclear complexes of the tris(catecholamide)derivative of a tetraazamacrocycle with Fe~(3+),Cu~(2+)and Zn~(2+)metal ions

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