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Synthesis of tetrapyrrolic N-confused porphyrinoids and exploration their function

四吡咯氮杂卟啉类化合物的合成及其功能探讨

基本信息

批准号：
16350024
负责人：
FURUTA Hiroyuki
金额：
$ 10.05万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

To explore the chemistry of "N-confused porphyrinoids" that has been started from the finding of N-confused porphyrin, metal coordination of NCP and synthesis of N-confused expanded porphyrins were mainly studied.When Re, a typical metal that can afford a tripodal complex, was subjected for the metal coordination to an NCP ligand, unusual N-fused porphyrin Re complex, whose confused pyrrole ring is inverted and fused to an adjacent pyrrole ring in the porphyrin core, was obtained. This complex we further oxidized to afford a Re trioxo-complex, which catalyzed an oxygen transfer reaction efficiently.In the synthesis of the confused expanded porphyrins, several new confused octaphyrins and their complexes were obtained. From the x-ray analysis of the octaphyrin complexes, the release of the strain energy by the introduction of confused pyrrole rings was suggested. Furthermore, several new features including near infrared emission and multi-redox were revealed with the doubly confused hexaphyrin complexes.On the other hand, a different type of confused porphyrin such as pyrazole porphyrin was newly synthesized. The synthetic methodology is thought applicable to other multi-confused porphyrins.

为了探索由发现N-混乱卟啉而开始的“N-混乱卟啉类化合物”的化学性质，本论文主要研究了NCP的金属配位和N-混乱卟啉的合成，将具有三脚架结构的典型金属铼（Re）与NCP配体进行金属配位，得到一种罕见的N-稠合卟啉铼配合物，其混乱的吡咯环被倒置并稠合到卟啉核中的相邻吡咯环上。该配合物进一步氧化得到了铼的三氧配合物，该配合物有效地催化了氧转移反应。在混乱膨胀卟啉的合成中，得到了几种新的混乱八卟啉及其配合物。从八卟啉配合物的X射线分析，通过引入混乱的吡咯环的应变能的释放被建议。此外，还发现了双混色六卟啉配合物具有近红外发射和多氧化还原等新的性质。另一方面，还合成了一种新的混色卟啉化合物，如吡唑卟啉。该合成方法适用于其他多杂卟啉化合物的合成。