双核金属卟啉的合成及其催化羟基化环己烷的研究

SYNTHESIS OF METALLIC COMPLEXES OF BISPORPHYRINS AND THEIR CATALYTIC REACTIONS OF CYCLOHEXANE

合成了以乙基、丙基、丁基在卟啉 5 ,5′ 苯基邻位通过醚键联结的不同链长的双核金属铁 (Ⅲ )、锰 (Ⅲ )卟啉 ,并用NMR、元素分析和UV Vis光谱进行了验证。以它们为催化剂 ,亚碘酰苯为氧化剂获得氧化环己烷的最好产率 ,环己醇为 35 83% ,环己酮为 2 3 41%。通过产率比较 ,初步定性地获得了双核金属卟啉的活性和稳定性的规律 ,即双铁亚乙基卟啉 >双铁亚丙基卟啉 >双铁亚丁基卟啉 >单铁卟啉和单锰卟啉 >双锰亚丁基卟啉 >双锰亚丙基卟啉 >双锰亚乙基卟啉 ,由于相同的条件下铁和锰的规律相反 ,推测在双卟啉模型中存在着金属之间的相互作用 。

Several new metallic iron(Ⅲ) and manganese(Ⅲ) bisporphyrins bonded with chain of different length at ortho position of phenyl of 5,5′ of porphrin were was synthetized and tested by spectrum of NMR,elemental analysis and UV Vis spectra.With these model compounds as catalyses and iodosobenzene as oxidant,iniatial and equilium yields of oxidative reactions of cyclohexane were conducted.The best yields of cyclohexanol and cyclohexanone were 35.83% and 23.41% respectively.From the data of yields,the sequence of activity and stability of these metallic bisporphyrins complexes were explored qualitatively as BFEP(13)>BFPP(15)>BFBP(17)>MFP(11) and MMP(12)>BMBP(18)>BMPP(16)>BMEP(14).It was found at the same situation iron manganese had adverse sequence.Thus there was metal metal interaction in the matallic irons and manganeses in matallic bisporp hyrins.Furthmore the effet was adverse to iron and manganese.