Structure and Chemistry of N-Substituted Corroles and Their Rhodium(I) and Zinc(II) Metal-Ion Complexes

Liliya Simkhovich; Parameswar Iyer; Israel Goldberg; Zeev Gross

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Structure and Chemistry of N-Substituted Corroles and Their Rhodium(I) and Zinc(II) Metal-Ion Complexes

机译：N取代的芳族化合物及其铑（I）和锌（II）金属离子配合物的结构和化学

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In the present work we report on the detailed structural features of the chiral N~21-and N~22-substituted benzyl and picolyl derivatives of tris(penta-fluorophenyl)corrole [H_3(tpfc)]. The main diffeence between the isomers is that substitution on N~22 creates a much more crowded environment, reflect ed in higher deformation of the corrole ring from planarity and of the meso-aryls from perpendicular orientation. The effects of metal-ion chelation on corrole geometry are demonstrated by structural investigations of the Zinc(II) and rhodium(I) complexes of the N~(21)-and N~22-alkylated corroles. The major finding is the intramlecular corrdination of the pyridine moiety of the picolyl substituent in the case of [Zn~(II)(N~21-picolyl-tpfc)]. This pyridine is readily attracted to the zinc ion as an axial ligand, thus replacing the externaly pyridine molecule of the precursor [Zn~(II)(N~21-benzyl-tpfc)(py)]. The change is associated with a considerable flattening of the corrole ring in order to allow a more convenient coordination of the zinc ion to all four pyrrole nitrogen atoms (at Zn-N(pyrrole) distances of 1.956-1.987 A for the nonsubstituted sites, and 2,224-2.247A for the substituted sites). These structural investigations also aid a good understanding of the spectroscopic characteristics of the derivatives.

机译：在本工作中，我们报告了三（五氟苯基）甲酸酯[H_3（tpfc）]的手性N〜21和N〜22取代的苄基和甲基吡啶衍生物的详细结构特征。异构体之间的主要区别是在N〜22上的取代产生了一个更为拥挤的环境，反映在平面性和垂直方向上的芳基和芳基的较高变形中。通过对N〜（21）-和N〜22-烷基化的腐蚀物的锌（II）和铑（I）配合物进行结构研究，证明了金属离子螯合对腐蚀物几何形状的影响。主要发现是在[Zn〜（II）（N〜21-picolyl-tpfc）]的情况下，甲基吡啶基的吡啶部分的分子内corcording。该吡啶很容易作为轴向配体被锌离子吸引，从而取代了前体[Zn〜（II）（N〜21-苄基-tpfc）（py）]的外吡啶分子。该变化与铁氧体环的显着变平有关，以便允许锌离子与所有四个铁氧体氮原子（在非取代位点的锌-N（吡咯）距离为1.956-1.987 A时）更方便配位，并且2,224-2.247A（替换位点）。这些结构研究还有助于对衍生物的光谱特性有很好的了解。

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《Chemistry: A European journal》 |2002年第11期|共7页
作者
Liliya Simkhovich; Parameswar Iyer; Israel Goldberg; Zeev Gross;
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chelates; chirality; corroles; rhodium; zinc;

机译：螯合物;手性;花键;铑;锌;

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1. Structure and Chemistry of N-Substituted Corroles and Their Rhodium(I) and Zinc(II) Metal-Ion Complexes [J] . Liliya Simkhovich, Parameswar Iyer, Israel Goldberg, Chemistry: A European journal . 2002,第11期

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Structure and Chemistry of N-Substituted Corroles and Their Rhodium(I) and Zinc(II) Metal-Ion Complexes

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