철(II)의 착체에 의해 촉매작용된 기질의 산소 활성화

박봉진; 이용희; Bong Jin Park; Yong Hee Lee

Journal of the Korean Industrial and Engineering Chemistry, Vol.13, No.5, 403-406, August, 2002

Export Citation

철(II)의 착체에 의해 촉매작용된 기질의 산소 활성화

Oxygen Activation of Substrate Catalyzed by Ferrous Complexes

박봉진, 이용희^{1, †}

롯데제과(주), 서울 150-964
¹동아대학교 기초과학연구소, 부산 614-714

Bong Jin Park, and Yong Hee Lee^{1, †}

LOTTECONFECTIONERY Co. Ltd., Seoul 150-964, Korea
¹Basic Science Research Institute, Dong-A University, Busan 614-714, Korea

E-mail:

초록

Fe(II)촉매하에서 O2에 의한 기질의 산화는 헴(heme)에 의해 이루어진 가역산화 때문에 생물학적 흥미가 대단해서, 본 연구는 리간드로써 pyridine이나 amide 같은 염기의 존재하에서 착체하는 리간드인 ferrous-perchlorate와 전해질로써 혼합 lithium-perchlorate에 의해 형성된 Fe(II)-acetylacetone과 Fe(II)-salicylaldehyde에 의하여 야기된 산화반응의 증거를 나타내고, 비수용매를 포함한 폭넓은 용매범위 및 Fe(II)의 각각 다른 농도들에서 과량인 리간드의 적당한 조건들하에서 산화를 살펴본다. 그 반응은 비라디칼 메카니즘으로 일어나는 것을 알았다.

Oxidation of a substrate by molecular oxygen in the presence of Fe(II) catalysts is of great biological interest in view of the reversible oxidation effected by heme. We report here the evidence of an oxidation reaction that formed Fe(II)-acetylacetone and Fe(II)-salicyladehyde. The oxidation reaction was caused by the ligands, ferrous-perchlorate, that exists in the presence of a base, pyridine or amide, with mixed lithium-perchlorate as the supporting electrolyte. In this study, under optimal conditions a wide range of solvents (DMA, DMF, acetonitrile, acetone, and ethanol), which included non-aqueous solvents, and various concentrations of Fe(II) were used to investigate the oxidation of excess ligand. The oxidation reaction appeared to take place by a nonradical mechanism.

Keywords:oxidation reaction;Fe(II)-acetylacetone;Fe(II)-salicylaldehyde;base;nonradical mechanism

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[1] Collman JP, Gagne RR, Halbert TR, Marchon JC, Reed CA, J. Am. Chem. Soc., 95, 7868 (1973)

[2] Almog J, Baldwin JE, Huff J, J. Am. Chem. Soc., 97, 227 (1975)

[3] Traylor TG, Campbell D, Tsuchiya S, J. Am. Chem. Soc., 101, 4748 (1979)

[4] Dhar SK, Abdelaziz J, Cozzi P, Jasien P, Mason C, Zalenas R, J. Am. Chem. Soc. Chem. Commun., 8 (1984)

[5] Khar SK, Park BJ, Arnold C, Microchem. J., 47, 14 (1993)

[6] Herron N, Busch DH, J. Am. Chem. Soc., 103, 1236 (1981)

[7] Hanzlik RP, Williamson D, J. Am. Chem. Soc., 98, 6570 (1976)

[8] Sheldon RA, Kochi JK, Metal Ion Catalyzed Oxidation of Organic Compounds, Academic Press, New York (1981)

[9] Sawyer DT, Chiericato C, Angelis CT, Nanni EJ, Tsuchiya T, Anal. Chem., 54, 1720 (1982)

[10] Sheau C, Sobkowisk A, Jeon S, Sawyer DT, J. Am. Chem. Soc., 112, 879 (1990)