• 제목/요약/키워드: Binuclear complex

검색결과 35건 처리시간 0.029초

Epoxidation of Olefins by Iodosylbenzene Catalyzed by Non-Porphyrin Metal Complexes

  • Nam Wonwoo;Baek Seung Joong;Kazuko I. Liao;Joan Selverstone Valentine
    • 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.

Syntheses and Crystal Structures of Xylyl-Bridged NO2S2-Donor Macrocycles and Binuclear Mercury(II) Complex

  • Lee, Ji-Eun;Jin, Yong-ri;Seo, Joo-beom;Yoon, Il;Song, Mi-Ryoung;Lee, So-Young;Park, Ki-Min;Lee, Shim-Sung
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.203-207
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    • 2006
  • Isomeric series of dilinked $NO_2S_2$ macrocycles ($L^2$: para-, $L^3$: meta- and $L^4$: ortho-linked) capable of binuclear complexing ability were prepared from its monomeric analog $L^1$ in reasonable yields except ortho-type reaction, which led to mixture due to the formation of monomer-type macrocyclic quaternary ammonium bromide $L^5$. Moreover, L2 (as $2HNO_3$ form) and $L^5$ were confirmed by an X-ray crystallography. Reaction of $HgCl_2$ with $L^2$ yielded a binuclear complex $[Hg_2(L^2)Cl_4]$. In the complex, each mercury(II) has a distorted tetrahedral environment made up of S and N donors from an exodentate $L^2$ and two coordinated Cl atoms.

한개의 산소다리를 가진 몰리브덴 (V) 착물의 산소고리화반응 (I). 아세톤 수용매에서 용매물과 $[Mo_2O_3(bipy)_2(NCS)_4]$ 의 반응 (Oxygen Ring Formation Reaction of Monoxo-Bridged Binuclear Molybdenum (V) Complexes (I). Reaction of $[Mo_2O_3(bipy)_2(NCS)_4]$ with Solvent Water in Aqueous Acetone Mixture)

  • 오상오;권진기;김창수
    • 대한화학회지
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    • 제30권4호
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    • pp.345-351
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    • 1986
  • 아세톤수용액에서 한개의 산소가 다리로된 이핵물리브덴(V)착물인 $[Mo_2O_3(bipy)_2(NCS)_4]$는 이옥소다리이핵몰리브덴(V)착물인 $MoO_4(bipy)_2(NCS)_2$를 생성한다. $[Mo_2O_3(bipy)_2(NCS)_4]$에서 $MoO_4(bipy)_2(NCS)_2$로 바꾸어 지는 속도는 분광광도법으로 측정하였다. 용매 물과 이옥소다리이핵몰리브덴(Ⅴ)착물의 생성속도는 속도법칙, 속도= k$[Mo_2O_3(bipy)_2(NCS)_4]\;[H_2O]$에 따른다. 이옥소다리착물의 생성반응메카니즘에 대해서 논의된다. 관찰된 음의 활성화부피는 착물이 용매분자를 전이상태에서 강하게 당길 것으로 보인다.

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$Fe^{II}-Co^{III}$이핵착물의 광유발 전자이동반응 (Light-Induced Electron Transfer Reactions in FeⅡ-CoⅢ Binuclear Complexes)

  • 이규환
    • 대한화학회지
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    • 제38권8호
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    • pp.598-602
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    • 1994
  • 이핵착물 $(NC)_5FeII-L-CoIII(NH_3)_5$ 분자내에서의 광유발 전자이동반응을 정류상태 광분해 실험으로 조사하여 속도상수를 결정하고 다리리간드 L의 종류에 따른 영향을 고찰하였다. 금속 결합자리 사이에 콘쥬게이션이 유지되는 BP, PHEN, DAP 리간드는 klight가 약 $3{\times}10^{-2} sec^{-1}$, 양자수율이 상한값인 1이였으며 콘쥬게이션이 유지되지 못하는 BPEA리간드인 klight가 약 $2{\times}10^{-4} sec^{-1}$, 양자수율이 0.03으로 측정되었다. 이로부터 광유발 전자이동반응이 전하이동 들뜬 상태 MLCT*를 거치는 "화학적 메카니즘"인 것으로 증명하였다.

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