Chemistry of iron 10-heterocorroles

铁10-杂咯化合物的化学性质

• 批准号: 248847498
• 负责人: Professor Dr. Martin Bröring
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/248847498?language=en
• 关键词: Chemistry; iron; 10; heterocorroles

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.

10-杂环是本课题组最近合成的一类大环化合物。这些卟啉类似物最耐人寻味的特征在于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来微调。结合位大小的不同直接影响这些配体金属络合物的电子结构。第一个关于铁配合物的结果表明，改变的电子特征不仅导致了独特的光谱模式，而且似乎反映在新的反应性轮廓中。在本项目中，将制备10位氧、硫、硒和氮杂原子的10-杂角模型配体的铁配合物，并从其独特的电子结构(穆斯堡尔谱、EPR光谱、SQUID磁学)进行详细的表征。然后将系统地研究这些络合物的反应性作为N4结合位置大小的函数。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用途，以及在高氧化态下稳定铁的可能适用性。

项目成果

Heterocorrole Conformations: Little Saddling, Much Ruffling.

• DOI: 10.1002/anie.201705551
• 发表时间: 2017-08
• 期刊: Angewandte Chemie
• 作者: J. Roesner;Birte Cordes;Stefan Bahnmüller;Gabor Homolya;Dimitri Sakow;Peter Schweyen;R. Wicht;M. Bröring