• Title/Summary/Keyword: TMEDA

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Redox Chemistry and Valence Tautomerism of Cobalt-Quinone Complexes in Nonaqueous Solvents

  • 전승원;이현;이효경;최용국;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.212-217
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    • 1998
  • The electrochemistry and valence tautomerism of CoⅢ(N-N)(SQ)(Cat), [N-N=N,N,N',N'-tetramethylethylenediamine (TMEDA); SQ=3,5- or 3,6-di-tert-butyl-semiquinone, Cat=3,5- or 3,6-di-tert-butyl-catechol], have been investigated by spectroscopic, electrochemical, spectroelectrochemical methods in nonaqueous solvents under anaerobic condition. The transition temperature between tautomers is dependent upon the donation effect of substituted quinone ligand and solvent. It increases with the increase of donation effect of solvent and quinone ligand. CoⅢ(TMEDA)(SQ)(Cat) is reduced to [CoⅡ(TMEDA)(SQ)(Cat)]-, and then reduces to [CoⅡ(TMEDA)(Cat)2]2-. CoⅢ(TMEDA)(SQ)(Cat) is oxidized to [CoⅢ(TMEDA)(SQ)2]+, but the stability of the oxidized form in DMF is dependent upon the solution temperature. With the increase of solution temperatrue the oxidized form may be converted to [CoⅡ(TMEDA)(SQ)(BQ)]+ by intramolecular electron transfer from SQ ligand to CoⅢ.

Facile Precipitation Method for Morphological Tuning of Cu2O Crystals

  • Cho, Young-Sik;Huh, Young-Duk
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3239-3243
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    • 2014
  • We have developed a simple method for tuning the morphologies of $Cu_2O$ microcrystals. $Cu_2O$ microcrystals were prepared by precipitation at room temperature from a mixture of $Cu(CH_3COO)_2{\cdot}H_2O$, N,N,N',N'-tetramethyl ethylenediamine (TMEDA), ascorbic acid, and polyethylene glycol (PEG). TMEDA was used to promote the formation of copper-TMEDA complexes. A variety of $Cu_2O$ microcrystal morphologies were obtained simply by varying the concentrations of TMEDA and ascorbic acid. Aggregated $Cu_2O$ microspheres are formed at higher concentrations of ascorbic acid in the absence of TMEDA. Aggregated $Cu_2O$ microcubes are formed at lower concentrations of ascorbic acid and higher concentrations of TMEDA. The crystal growth mechanism of these $Cu_2O$ morphologies is explained.

TMEDA Catalyzed Henry (Nitroaldol) Reaction under Metal and Solvent-free Conditions

  • Majhi, Anjoy;Kadam, Santosh T.;Kim, Sung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.30 no.8
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    • pp.1767-1770
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    • 2009
  • The Henry (nitroaldol) reaction proceeds under mild conditions with catalytic amount of tetramethylethylenediamine (TMEDA) to afford $\beta$-nitro alkanol in considerably excellent yield. Structurally diverse aldehydes react with nitromethane in presence of 0.3 equiv of TMEDA under solvent-free condition at rt. The low catalytic loading and mild reaction condition are the key features of the catalytic method.

TMEDA: Efficient and Mild Catalyst for the Acylation of Alcohols, Phenols and Thiols under Solvent-free Condition

  • Kadam, Santosh T.;Lee, Han-Bin;Kim, Sung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.30 no.5
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    • pp.1071-1076
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    • 2009
  • N,N,N′,N′-tetramethylethylenediamine (TMEDA) acts as a simple, mild and efficient catalyst for the acylation of alcohols, phenols and thiols at room temperature under solvent-free condition. Acylation reaction with acetic anhydride and benzoic anhydride proceeds with good to excellent yield in the presence of TMEDA as the catalyst.

Synthesis of Alkylidyne Complexes of Br$(CO)_2(tmeda)M{\equiv}CC_{6}H_{4}Me$ (M = Cr, Mo, W). Crystal Structure of Br$(CO)_2(tmeda)M{\equiv}CC_{6}H_{4}Me$

  • Park, Joon T.;Cho, Jeong-Ju;Suh, Il-Hwan;Lee, Jin-Ho;Lim, Sung-Su;Ryu, Bo-Young
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.266-271
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    • 1993
  • The reaction of $(CO_5$)M=C(OMe)Tol (M=Cr, Mo, W and $Tol=p-C_6H_4Me)$ and $BBr_3$ followed by treatment with tetramethylethylenediamine (TMEDA) yields a mixture of two diastereomers, trans, $cis-Br(CO)_2(tmeda)M{\equiv}$CTol [M=Cr(1a), Mo(2a), W(3a)] and cis, $trans-Br(CO)_2(tmeda)M{\equiv}$CTol [M=Cr(1b), Mo(2b), W(3b)], respectively. These compounds have been isolated as crystalline solids and characterized by spectroscopic (infrared, mass, $^1H$ and $^{13}C-NMR)$ data. The trans, cis-Br(CO)2(tmeda)Cr${\equiv}$CTol (1a), has been examine via a single crystal X-ray diffraction study : $BrCrO_2N_2C_{16}H_{23}$, Mr=407.27, triclinic, $P{\bar{1}},\;a=12.792(2),\;b=13.400(5),\;c= 11.645(4)\;{\AA},\;{\alpha}=101.26(2)^{\circ},\;{\beta}=103.04(2)^{\circ},\;{\gamma}=91.88(2)^{\circ},\;{\nu}=1907(1){\AA}^3,\;Z=2,\;{\rho}(calcd)=1.418\;gcm^{-3},\;{\lambda}(MoK{\alpha})=0.71069\;{\AA},\;{\mu}=26.25 cm^{-1},\;F(000)=831.97,\;T=295K,\;R=0.0977$ for 1332 significant reflections $[F_0>5{\sigma}(F_0)]$. There are two essentially equivalent molecules in the crystallographic asymmetric unit. Each molecule is octahedral with the bromide ligand trans to the alkylidyne carbon, the two cis-carbonyl ligands, and the bidentate TMEDA ligand.

First Hydrogelation of Discrete Metal Complexes. Structures and Fluxional Behavior of Cyclopalladium(II) Complexes

  • Na, Young-Mee;Noh, Tae-Hwan;Ha, Byung-Jo;Hong, Jong-Ki;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.3
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    • pp.573-576
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    • 2009
  • The reaction of $(en)Pd(NO_3)_2$ (en = ethylenediamine) with 1,4-bis(dimethyl-4-pyridylsilyl)benzene (L) affords cyclodimer, $[(en)Pd(L)]_2(NO_3)_4$, whereas the reaction of $(tmeda)Pd(NO_3)_2$ (tmeda = N,N,N’,N’-tetramethylethylenediamine) with L gives cyclotrimer, $[(tmeda)Pd(L)]_3(NO_3)_6$. Both complexes exist as catenane in water. The catenated cyclodimer is rigid whereas the catenated cyclotrimer is dynamic in water. The catenated cyclotrimers afford hydrogel containing 98.5% water below 2 ${^{\circ}C}$. The hydrogel changes to its sol around 38 ${^{\circ}C}$, and to its clear solution at 78 ${^{\circ}C}$. Such a notable difference between $[(en)Pd(L)]_2(NO_3)_4$ and $[(tmeda)Pd(L)]_3(NO_3)_6$ might be explained by their different dynamic behavior via ring size effects.

Development of Optimal Bio-encapsulated Media for Organic/Inorganic Odor Reduction (유.무기성 악취저감을 위한 최적의 미생물 포괄고정담체 제조법에 관한 연구)

  • Kim, Sun-jin;Kim, Tae-Hyeong;Lee, Yun-Hee;Jang, Hyun-Sup;Song, Ji-Hyeon;Hwan, Sun-Jin
    • Journal of Korean Society of Water and Wastewater
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    • v.26 no.1
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    • pp.29-35
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    • 2012
  • A bio-encapsuled media was developed to apply on reducing odors produced from organic waste treatment process. The microorganism, candida tropicalis, was encapsulated in sponge media consisted of polyurethane material. Sodium alginate as a natural polymer which does not affect to hydrophilic microbes and PEGDA(poly ethylene glycol diacrylate) as a artificial polymer were used for the encapsuled media. The media was evaluated with TMEDA (N,N,N',N'-tetramethylethylenediamine, 0.02~0.1%) as a catalyst at different temperature 25 and $35^{\circ}C$. The best performance was achieved with 0.02% of TMEDA at $25^{\circ}C$. The microbes' activity in the media was examined by Live/Dead cell method.

Swellable Submicrospheres of Ionic Palladium(II) Complexes Containing Decylmethylbis(m-pyridyl)silane

  • Ryu, Yoon-Kyong;Kim, Cho-Rong;Kim, Chi-Won;Noh, Tae-Hwan;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2338-2340
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    • 2009
  • Ionic palladium(II) complex containing a long aliphatic chain, [(tmeda)$PdL]_2(PF_6)_4$ (tmeda = N,N,N',N'-tetramethylethylenediamine; L = decylmethylbis(m-pyridyl)silane) allowed to form a puckered submicrosphere morphology without any template or additive. The puckered spheres reversibly adsorb and desorb dioxane molecules. Coligand and cosolvent effects on the formation of submicrospherical morphology were observed.

Preparation of ZnO Thin Films Using Zn/O-containing Single Precursorthrough MOCVD Method

  • Park, Jong-Pil;Kim, Sin-Kyu;Park, Jae-Young;Ok, Kang-Min;Shim, Il-Wun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.1
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    • pp.114-118
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    • 2009
  • A new Zn/O single source precursor, TMEDA-Zn$(eacac)_2$, has been synthesized by using N, N, N’, N’-tetramethylethylendiamine (TMEDA), sodium ethyl-acetoacetate, and $ZnCl_2$. From this organometallic precursor, ZnO thin films have been successfully grown on Si (100) substrates through the metal organic chemical vapor deposition (MOCVD) method at relatively mild conditions in the temperature range of 390~430 ${^{\circ}C}$. The synthesized ZnO films have been found to possess average grain sizes of about 70 nm with an orientation along the c-axis. The precursor and ZnO films are characterized through infrared spectroscopy, nuclear magnetic resonance spectroscopy, EI-FAB-spectroscopy, elemental analyses, thermal analysis, X-ray diffraction, and field emission scanning electron microscopic analyses.