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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 39, Number 5
JKCSEZ 39(5)
October 20, 1995 

 
Title
Catalytic Activity of Ga(Ⅲ)-, In(Ⅲ)- and Tl(Ⅲ)-porphyrin Complexes
Author
Yu Chul Park*, Hun Gil Na, Seong Su Kim
Keywords
Abstract
비산화-환원 금속인 Ga(Ⅲ), In(Ⅲ), Tl(Ⅲ)d을 포함하는 금속 포르피린을 촉매체로 NaOCl을 산화제로 하여 올레핀의 촉매적 산화반응을 CH2Cl2에서 연구하였다. 포르피린은 (p-CH3O)TPP, (p-CH3)TPP, TPP, (p-F)TPP, (p-Cl)TPP 그리고 (F20)TPP를 사용하였다. 올레핀은 (p-CH3O)-, (p-CH3)-, (p-H)-, (p-F)-, (p-Cl)-, (p-Br)styrene 그리고 cyclopentene, cyclohexene을 사용하였다. 올레핀 산화반응에서 기질의 전환율(%)은 금속 포르피린 및 기질의 치환기 효과와 중심 금속이온 성질에 따라 고찰하였다. TPP 치환기에 따른 전환율의 변화는 p-CH3O < p-CH3 < H < p-F < p-Cl 순서로 증가하였다. 이러한 증가는 TPP의 4σ값의 증가 순서와 일치하였다. 기질의 치환기에 따른 전환률의 변화는 p-CH3O > p-CH3 > H > p-Cl > p-Br 순서로 치환기의 σ+값이 증가할수록 오히려 감소하였다. 올레핀의 산화 반응에서 In(Ⅲ)-, Tl(Ⅲ)-포르피린은 Ga(Ⅲ)-포르피린에 비하여 높은 촉매 활성을 나타내었다.

The catalytic oxidations of several olefins in CH2Cl2 have been investigated using non-redox metalloporphyrin (M=Ga(Ⅲ), In(Ⅲ), Tl(Ⅲ)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were (p-CH3O)TPP, (p-CH3)TPP, TPP, (p-F)TPP, (p-Cl)TPP and (F20)TPP (TPP=tetraphenylporphyrin), and olefins were (p-CH3O)-, (p-CH3)-, (p-H)-, (p-F)-, (p-Cl)- and (p-Br)styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of p-CH3O < p-CH3 < H < p-F < p-Cl, which was consistent with the sequence of 4σ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the σ+ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(Ⅲ)- and Tl(Ⅲ)-porphyrins turned out to be more active catalysts than Ga(Ⅲ)-porphyrin.

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364 - 370
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