权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Synthesis, properties, and reactivities of nonplanar ferric porphyrin complexes carrying rotationally coordinated axial ligands.

携带旋转配位轴向配体的非平面铁卟啉配合物的合成、性质和反应性。

基本信息

批准号：
07640732
负责人：
NAKAMURA Mikio
金额：
$ 1.47万
依托单位：
TOHO UNIVERSITY SCHOOL OF MEDICINE
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

We have observed that the electon configuration of iron in ferric porphyrin complexes changes from the usual (dxy)^2(dxz, dyz)^3 to unusual (dxz, dyz)^4(dxy)^1 as the deformation of the porphyrin ring increases in the following two systems.A series of bis (imidazole) (meso-tetraalkylporphyrinatoiron (III)) complexes, where R=Me, Et, and iPr, have been prepared. The crystallographic analysis of the ethyl complex has revealed that the porphyrin ring is highly S_4 ruffled. While the ^1H NMR signal of the pyrrole protons in the unsubstituted complex appears at a normal high field region as a low spin complex, those of the alkyl substituted complexes are observed at rather low field. Particularly in the isopropyl complex, the pyrrole signals appear at so called "diamagnetic region". Furthermore, the EPR of the isopropyl complex shows unusual "axial type" spectra. Based on these results, we concluded that the electronic configuration of iron in these complexes changes from the usual (dxy)^2(dxz, dyz)^3 to the unusual (dxz, dyz)^4(dxy)^1 as the nonplanarity of the porphyrin ring increases.A series of bis (cyanide) (meso-tetraalkylporphyrinatoiron(III)) complexes, where R=H,Me, Et, and iPr, have been prepared and examined by ^1H NMR,^<13>C NMR,and EPR spectra. While the unsubstituted complex (R=H) showed spectropic results similar to those of the typical low spin complexes, the alkyl substituted complexes exhibited quite different results ; pyrrole 1H and cyanide ^<13>C signals showed rather small paramagnetic shifts. Corresponding to the NMR results, the EPR of the alkyl substituted complexes gave the unusual "axial type" spectra instead of the usual "large gmax type" spectra. Based on these results, we concluded that the electronic configuration of iron in these complexes changes from (dxy)^2(dxz, dyz)^3 to (dxz, dyz)^4(dxy)^1 as the nonplanarity of the porphyrin ring increases.

在以下两个体系中，我们观察到铁卟啉配合物中铁的电子构型随着卟啉环形变的增加而从通常的（dxy）^2（dxz，dyz）^3变为不寻常的（dxz，dyz）^4（dxy）^1。乙基配合物的晶体学分析表明，卟啉环具有高度的S_4褶皱。未取代配合物中吡咯质子的^1H NMR信号在正常高场区出现，为低自旋配合物，而烷基取代配合物的^1H NMR信号在相当低的场区观察到。特别是在异丙基络合物中，吡咯信号出现在所谓的“抗磁区”。此外，异丙基配合物的EPR显示出不寻常的“轴型”光谱。根据这些结果，我们得出结论：随着卟啉环非平面性的增加，铁的电子构型从通常的（dxy）^2（dxz，dyz）^3转变为不寻常的（dxz，dyz）^4（dxy）^1。合成了一系列双（氰化物）（meso-四烷基卟啉合铁（III））配合物，其中R=H，Me，Et，iPr<13>。虽然未取代的配合物（R=H）显示出与典型的低自旋配合物相似的光谱结果，但烷基取代的配合物显示出完全不同的结果;吡咯1H和氰化物^<13>C信号显示出相当小的顺磁位移。与NMR结果相对应，烷基取代配合物的EPR谱给出了不寻常的“轴向型”谱，而不是通常的“大gmax型”谱。基于这些结果，我们得出结论：随着卟啉环的非平面性增加，这些配合物中铁的电子构型从（dxy）^2（dxz，dyz）^3变为（dxz，dyz）^4（dxy）^1。