Study of Synthesis and Physical Properties of New Porpyrin Compounds Incorporating Ferrocene Ring

卟啉类化合物是有机化学中最具吸引力的化合物之一，有望具有新的物理性质。我们研究了在二茂铁环的介晶位置引入二茂铁环的新的卟啉化合物的合成。最初我们尝试用未取代的吡咯作为起始剂，但容易发生聚合反应。然后用3-乙基-4-甲基吡咯取代吡咯。以[2+2]卟啉为原料合成了5，15-二茂铁基卟啉化合物，该化合物在卟啉环的中位面对面含有两个二茂铁环。此外，为了比较二茂铁取代的卟啉的物理性质，还合成了位置相近的具有苯基和对二茂铁基苯基的类似类型的卟啉化合物。对这些化合物进行了~1H-核磁共振、紫外-可见光谱和循环伏安图的测定。~1H-核磁共振谱表明，二茂铁环影响了卟啉环的环电流，NH质子向高磁场移动，CH质子向低磁场移动。从UV-Vis光谱也可以看出，二茂铁环的存在会影响到二茂铁环的平面，这可能是由于二茂铁环的存在而引起的。含二茂铁基的卟啉的环图也显示出比通常的卟啉环低的电势位移，这意味着二茂铁取代的卟啉具有高的还原性能。合成了锌、钴、铁络合物，并对其物理性能进行了研究。

The porphyrin compounds are one of most attractive compounds in organic chemistry that are expected to have new physical properties. We have investigated about synthesis of new porphyrin compounds which is incorporating ferrocene rings at the meso position of porpyrin ring. At first we tried to use unsubstituted pyrrole as starting reagent, but polymerising were easily occurred. Then we used 3-ethyl-4-methyl pyrrole derivative instead of pyrrole. 5, 15-diferrocenyl porphyrine compound was prepared by using to [2+2]porupyrine synthesis, which have two ferrocene rings at face to face meso position of porphyrine rings. Furthermore, similar type of porphyrine compounds which have penyl and p-ferrocenylphenyl group substituted porupyrin compounds at the similar position were synthesized for comparing the physical properties of ferrocene substituted porphyrine. These compounds were measured ^1H-NMR, UV-VIS spectra , and also cyclicboltanogram. In ^1H-NMR spectrum, It was known that the ring current of porphyrin ring was influenced by the ferrocene ring, NH protones were shifted to high magnetic field and CH protons were shifted to low magnetic fields. From UV-VIS spectrum it was also known that the ferrocene ring were influenced to the planar of porphyrin ring, it may be distorted by exist of ferrocene ring. Cyclicboltanogram of porphyrin having ferrocene moiety also showed low potential shift compared of usual porphyrin ring, this mean ferrocen substituted porupyrine have high reductive properties. Zinc , cobalt and ferric complexes were synthesized, and physical properties were investigated.