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

卟啉化合物是有机化学中最具吸引力的化合物之一，有望获得新的物理性质。本文研究了在卟啉环的中位引入二茂铁环的新型卟啉化合物的合成。起初我们尝试用未取代的吡咯作为起始试剂，但容易发生聚合反应。然后用3-乙基-4-甲基吡咯衍生物代替吡咯。采用[2+2]卟啉合成法合成了5，15-双二茂铁基卟啉化合物。此外，为了比较二茂铁取代卟啉化合物的物理性质，还合成了在类似位置上有苯基和对二茂铁苯基取代的类似卟啉化合物。对这些化合物进行了~ 1H-NMR、UV-维斯光谱和循环伏安图的测定。在~ 1H-NMR谱中，卟啉环的环电流受二茂铁环的影响，NH质子向高磁场方向移动，CH质子向低磁场方向移动。从紫外-可见光谱还可以看出，二茂铁环的存在对卟啉环的平面有一定的影响，可能会使卟啉环的平面发生畸变。含二茂铁取代的卟啉的环伏安曲线也显示出较低的电位偏移，这意味着二茂铁取代的卟啉具有较高的还原性能。合成了锌、钴、铁的配合物，并对其物理性质进行了研究。

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.