METAL-COMPLEXES WITH TETRAPYRROLE LIGANDS .54. SYNTHESIS, SPECTRA, STRUCTURE, AND REDOX PROPERTIES OF CERIUM(IV) BISPORPHYRINATES WITH IDENTICAL AND DIFFERENT PORPHYRIN RINGS IN THE SANDWICH SYSTEM
METAL-COMPLEXES WITH TETRAPYRROLE LIGANDS .54. SYNTHESIS, SPECTRA, STRUCTURE, AND REDOX PROPERTIES OF CERIUM(IV) BISPORPHYRINATES WITH IDENTICAL AND DIFFERENT PORPHYRIN RINGS IN THE SANDWICH SYSTEM
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DOI：
10.1002/cber.19891221203
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发表时间：
1989-12-01
期刊：
影响因子：
--
通讯作者：
WEISS, R
中科院分区：
文献类型：
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作者：
BUCHLER, JW;DECIAN, A;WEISS, R
由乙酰丙酮铈（III）和四苯基卟啉、四-对-氯苯基卟啉和十六氢四苯并卟啉制备另外的对称的二卟啉铈（IV）酸盐。在后一种情况下，还发现了双铈（III）三层德克尔，这是八甲基卟啉情况下的唯一产物。从两种不同卟啉的混合物，即八乙基卟啉[H2（OEP）]和四苯基卟啉[H2（TPP）]或四-对-氯苯基卟啉[H2（TClP）]，除了对称物种Ce（OEP）2和Ce（TPP）2之外，还获得不对称（“混合”）双层Ce（OEP）（TPP）或Ce（OEP）（TClP），其在夹心体系中具有不同的卟啉环，并且可以通过色谱法分离。Ce（OEP）（TPP）的晶体结构分析显示CeIV为卟啉环的吡咯N原子的正方反棱柱几何形状。虽然不对称双层卟啉的IR和NMR光谱是各个环光谱的叠加，但它们的UV/维斯光谱和循环伏安图表明两个卟啉环表现为共同的π电子系统。还描述了π-阳离子自由基盐[Ce（OEP）2] ClO 4和[Ce（OEP）（TPP）] SbCl 6的制备。在后者中，缺陷电子似乎优先驻留在OEP环中。
Further symmetrical cerium(IV) bisporphyrinates are prepared from cerium(III) acetylacetonate and tetraphenylporphyrin, tetra‐p‐chlorophenylporphyrin, and hexadecahydrotetrabenzporphyrin. In the latter case, a biscerium(III) triple‐decker is also found which is the only product in the case of octamethylporphyrin. From a mixture of two different porphyrins, namely octaethylporphyrin [H2(OEP)] and either tetraphenylporphyrin [H2(TPP)] or tetra‐p‐chlorophenylporphyrin [H2(TClP)], besides the symmetrical species Ce(OEP)2and Ce(TPP)2, the unsymmetrical (“mixed”) double‐deckers Ce(OEP)(TPP) or Ce(OEP)(TClP) are obtained which have different porphyrin rings in the sandwich system and can be separated by chromatography. The crystal structure analysis of Ce(OEP)(TPP) shows CeIVin a square‐antiprismatic geometry of the pyrrole N atoms of the porphyrin rings. While the IR and NMR spectra of the unsymmetrical double‐deckers are superpositions of the spectra of the individual rings, their UV/VIS spectra and cyclic voltammograms indicate that the two porphyrin rings behave as a common π‐electron system. The preparation of the π‐cation radical salts [Ce(OEP)2]ClO4and [Ce(OEP)(TPP)]SbCl6is also described. In the latter, the defect electron seems to reside preferentially in the OEP ring.