• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1112-1118
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• 1994

Epoxidation of olefins has been studied using iodosylbenzene (PhIO) as the terminal oxidant and binuclear and mononuclear complexes of $Mn^{2+}$, $Co^{2+}$, and $Cu^{2+}$ as catalysts. Epoxides were the predominant products with trace amounts of allylic oxidation products, and the metal complexes were found to be effective catalysts in the epoxidation reactions. The reactivity of binuclear copper complexes was greater than that of the mononuclear copper complexes, whereas the binuclear and mononuclear complexes of $Mn^{2+}$ and $Co^{2+}$ showed similar reactivities. The nature of the ligands bound to copper did not influence the reactivity of the binuclear copper complexes so long as copper ions were held in close proximity. A metal-iodosylbenzene complex, such as suggested previously for Lewis acidic metal complex-catalyzed epoxidation by iodosylbenzene, is proposed as the active epoxidizing species. Some mechanistic aspects are discussed as well.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.295-298
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• 2013

• 대한화학회지
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• 제36권5호
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• pp.709-719
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• 1992

이핵성 네자리 Schiff base 의 cobalt(II), nickel(II) 및 copper(II) 착물인 [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(L)_4] 및 [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO 및 DMF)들을 합성하여 원소분석, IR-spectrum, UV-visible spectrum, T.G.A. 및 D.S.C.를 측정하여 이핵성 착물로 주어짐을 확인하였다. 지지전해질로서 0.1M TEAP-L (L; Py, DMSO 및 DMF)에서 1mM-착물용액의 순환전압-전류법과 D.P.P.법으로 전기화학적 성질을 측정한 결과 이핵성 cobalt(II) 착물은 일전자의 확산 지배적인 네단계의 산화-환원과정이 Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 으로 일어나고 이핵성 nickel(II) 및 copper(II) 착물들은 일전자의 확산지배적인 두 단계의 산화-환원과정이 M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni 및 Cu)으로 일어남을 알았다.