Chemistry of iron 10-heterocorroles

10-杂环类大环化合物是本课题组最近合成的一类卟啉类大环化合物。这些卟啉类似物的最有趣的特征在于N4结合位点的几何形状，其大小可以通过在10位使用不同的杂原子进行微调。结合位点的大小直接影响这些配体的金属配合物的电子结构。本研究以10位上含有氧、硫、硒和氮杂原子的10-杂可咯模型配体为研究对象，制备了铁配合物，并对其电子结构进行了详细的表征（穆斯堡尔谱、EPR谱、SQUID磁强计）。然后将系统地研究这些复合物的反应性作为N4结合位点的大小的函数。特别令人感兴趣的是作为细胞色素c '的生物无机模型的潜在效用，以及用于稳定高氧化态铁的可能适用性。

10-Heterocorroles are a class of porphyrinoid macrocycles that have been made synthetically accessible recently in our group. The most intriguing feature of these porphyrin analogs lies in the geometry of the N4-binding site, whose size can be fine-tuned through the use of different heteroatoms at the 10-position. The different size of the binding site directly influences the electronic structure of metal complexes of these ligands. First results on iron complexes show that the altered electronic features lead not only to distinctive spectroscopic pattern, but also seems to be reflected in new reactivity profiles.In this project, iron complexes of 10-heterocorrole model ligands with oxygen, sulfur, selenium and nitrogen heteroatoms in the 10 position will be prepared and characterized in detail with respect to their unique electronic structures (Mössbauer, and EPR spectroscopy, SQUID magnetometry). The reactivities of these complexes will then be studied systematically as a function of the size of the N4 binding site. Of particular interest are a potential utility as a bioinorganic model for cytochrome c', and a possible suitability for the stabilization of iron in high oxidation states.