• Title/Summary/Keyword: transition metal complex

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Effects of the Transition Metal Oxides Substituted for Mg on the Electrical Conductivity of La0.8Sr0.2Ga0.8Mg0.2O3-δ -based Electrolytes (Mg에 치환된 전이금속이 La0.8Sr0.2Ga0.8Mg0.2O3-δ 고체전해질의 전기전도도에 미치는 영향)

  • Park, Sang-Hyoun;Yoo, Kwang-Soo
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.18 no.4
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    • pp.330-337
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    • 2005
  • La/sub 0.8/Sr/sub 0.2/Ga/sub 0.8/Mg/sub 0.2/O/sub 3-δ/-based solid electrolytes in which Mg site was partially substituted by Fe, Co or Ni (0.05, 0.1, 0.15 at.%) were fabricated by conventional solid-state reaction and their sintered densities were above 94% of theoretical density. X-ray diffraction analysis and microstructure observation for the sintered specimens were performed. The ac complex impedance were measured at 400。C to l000。C in air and fitted with a Solatron ZView program. The electrical conductivity of La/sub 0.8/Sr/sub 0.2/Ga/sub 0.8/Mg/sub 0.2/O/sub 3-δ/-based solid electrolytes substituted by Fe, Co or Ni was higher than that of pure La/sub 0.8/Sr/sub 0.2/Ga/sub 0.8/Mg/sub 0.2/O/sub 3-δ/. The electrical conductivity of La/sub 0.8/Sr/sub 0.2/Ga/sub 0.8/Mg/sub 0.05/Ni/sub 0.15/O/sub 3-δ/ electrolyte was 3.4×10/sup -2/ Scm/sup -1/ at 800。C and the highest value of the whole electrolytes.

A Density Functional Theory Investigation on Intramolecular Hydrogen Transfer of the [Os3(CO)11P(OMe)3(Ru(η5-C5H5))2] Cluster

  • Buntem, Radchada;Punyain, Kraiwan;Tantirungrotechai, Yuthana;Raithby, Paul R.;Lewis, Jack
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.934-940
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    • 2010
  • The reduction of [$Os_3(CO)_{11}P(OMe)_3$] and subsequent ionic coupling of the reduced species with $[Ru({\eta}^5-C_5H_5)(CH_3CN)_3]^+$ resulted in the formation of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$] which can be converted to spiked tetrahedral cluster, [$HOs_3(CO)_{11}P(OMe)_3Ru_2({\eta}^5-C_5H_5)(C_5H_4)$] via the intramolecular hydrogen transfer. Due to the unavailability of a suitable single crystal, the PW91/SDD and LDA/SDD density functional methods were used to predict possible structures and the available spectroscopic information (IR, NMR) of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$]. The most probable geometry found by constrained search is the isomer (a2) in which the phosphite, $P(OMe)_3$, occupies an axial position on one of the two osmium atoms that is edge bridged by the $Ru(CO)_2({\eta}^5-C_5H_5)$ unit. By using the most probably geometry, the predicted infrared frequencies and $^1H$, $^{13}C$ and $^{31}P$ NMR chemical shifts of the compound are in the same range as the experimental values. For this type of complex, the LDA/SDD method is appropriate for IR predictions whereas the OPBE/IGLO-II method is appropriate for NMR predictions. The activation energy and reaction energy of the intramolecular hydrogen transfer coupled with the structural change of the transition metal framework were estimated at the PW91/SDD level to be 110.32 and -0.14 kcal/mol respectively.

Characteristics Comparison of Prepared Films According to Influence of Adsorption Inhibitor in the Condition of Deposition (PVD증착용 흡착인히비터의 영향에 따른 제작막의 특성 비교)

  • 이찬식;윤용섭;권식철;김기준;이명훈
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2001.11a
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    • pp.67-67
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    • 2001
  • The structure zone model has been used to provide an overview of the relationship between the microstructure of the films deposited by PVD and the most prominent deposition condition.s. B.AMovchan and AV.Demchishin have proposed it firstls such model. They concluded that the general features of the resulting structures could be correlated into three zones depending on $T/T_m$. Here T m is the melting point of the coating material and T is the substrate temperature in kelvines. Zone 1 ($T/Tm_) is dominated by tapered macrograins with domed tops, zone 2 ($O.3) by columnar grains with denser boundaries and zone 3 ($T/T_m>O.5$) by equiaxed grains formed by recrystallization. J.AThomton has extended this model to include the effect of the sputtering gas pressure and found a fourth zone termed zone T(transition zone) consisting of a dense array of poorly defined fibrous grains. R.Messier found that the zone I-T boundary (fourth zone of Thorton) varies in a fashion similar to the film bias potential as a function of gas pressure. However, there has not nearly enough model for explaining the change in morphology with crystal orientation of the films. The structure zone model only provide an information about the morphology of the deposited film. In general, the nucleation and growth mechanism for granular and fine structure of the deposited films are very complex in an PVD technique because the morphology and orientation depend not only on the substrate temperature but also on the energy of deposition of the atoms or ions, the kinetic mechanism between metal atoms and argon or nitrogen gas, and even on the presence of impurities. In order to clarify these relationship, AI and Mg thin films were prepared on SPCC steel substrates by PVD techniques. The influence of gas pressures and bias voltages on their crystal orientation and morphology of the prepared films were investigated by SEM and XRD, respectively. And the effect of crystal orientation and morphology of the prepared films on corrosion resistance was estimated by measuring polarization curves in 3% NaCI solution.

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Availability of Heavy Metals in Soil and Their Translocation to Water Dropwort (Oenanthe javanica DC.) Cultivated near Industrial Complex (토양내 중금속 유효도와 미나리중의 흡수이행성 평가)

  • Jung, Goo-Bok;Kim, Won-Il;Lee, Jong-Sik;Shin, Joung-Du;Kim, Jin-Ho;Lee, Jeong-Taek
    • Korean Journal of Environmental Agriculture
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    • v.25 no.4
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    • pp.323-330
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    • 2006
  • This experiment was conducted to investigate heavy metal transition and bioavailability from soil to the edible pare of water dropwort near industrial complex. The soils were collected from the paddies cultivating water dropwort stream sediments, and background soils near industrial complex. The pH values, organic matter, Av. $P_2O_5$, Ex. Ca content of paddy soils were higher than those measured for nor-contaminated paddy fields in 2003. The contents of Cd and Cu was higher than those of standard level for soil contamination by Soil Environmental Conservation Act in Korea. The pollution index in stream sediments were higher than those of paddies cultivating water dropwort. The geoaccumulation index of heavy metals in paddy soils and stream sediment were in the order Cu>Cd>Ni>Zn>Pb. The rates of 0.1N-HCl extractable heavy metals to total contents in soils were in the order Cd>Cu>Zn>Ni>Pb. In case of Cd and Ni in paddy soils near industrial complex, 0.1N-HCl extractable heavy metals and total content were highly correlated with each other. Heavy metal contents in mot parts were higher than those in top pare of water dropwort. The Zn and Cu transfer factor from soil to the top pare of water dropwort were higher than those of other heavy metals. The bioavailability of water dropwort varied considerably between the different parts and heavy metals. Cd, Cu and Ni contents in water dropwort were correlated with each elements in paddy soils.

Fabrication and Its Characteristics of YSZ Composite with Added Transition Metal Oxides (천이금속산화물이 첨가된 YSZ 복합체의 제조 및 그 특성)

  • 최성운;박재성
    • Journal of the Institute of Electronics Engineers of Korea TE
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    • v.39 no.4
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    • pp.341-349
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    • 2002
  • Electrical, mechanical and sinterability properties of yttria-stabilized zirconia doped with 5.35wt% $Y_2$O$_3$(Y$_2$O$_3$- containing stabilized zirconia : YSZ) were studied as a function of $Al_2$O$_3$, CoO, Fe$_2$O$_3$ and MnO$_2$ addition. The ratio of monoclinic phase to tetragonal phase was changed by the addition of $Al_2$O$_3$, CoO, Fe$_2$O$_3$ and MnO$_2$ to 8.00 wt% and sintered density decreased with increasing $Al_2$O$_3$, CoO, Fe$_2$O$_3$ and MnO$_2$ addition. Fracture toughness increased with the increase of monoclinic to tetragonal phase ratio and was maximum at about 18%. When transition metals such as CoO, Fe$_2$O$_3$ or MnO$_2$ was added more than 1.5 wt%, the electrical conductivity of YSZ increased. But $Al_2$O$_3$ hardly affected the electrical conductivity of YSZ. The addition of $Al_2$O$_3$, CoO, Fe$_2$O$_3$ and MnO$_2$ into YSZ resulted in the more complex behavior of fracture toughness and hardness variation and the specimen with 1.5wt%-Fe$_2$O$_3$, 3.0wt%-Al$_2$O$_3$ and 1.5wt%-CoO showed the monoclinic to tetragonal phase ratio of 18% and the highest toughness of 10.8 MPa.m$^{1}$2/ and Vickers hardness of 1201 kgf/mm$^2$.

X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides (α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.38-45
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    • 2011
  • The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.

Polymerization of Hydrosilanes and Vinyl Monomers in the Presence of Transition Metal Complex

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Shin, Joong-Hyeok;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.2 no.1
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    • pp.18-23
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    • 2009
  • This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

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Effect of Transition Metal Ion on the Reaction of Benzylbromide with Grignard Reagent (Grignard 시약과 브로모벤질과의 반응에서 첨가전이 금속이온의 영향 연구)

  • Jack C. Kim;Young-Sim Koh;Ung-Chan Yoon;Min-Sook Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.228-236
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    • 1993
  • The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.

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Spectroscopic, Thermal and Biological Studies on Newly Synthesized Cu(II), Ni(II) and Co(II) Complexes with 3-N-2-hydroxyethylamine Benzanthrone and 3-N-2-aminoethylamine Benzanthrone (3-N-2-hydroxyethylamine benzanthrone 및 3-N-2-aminoethylamine benzanthrone에 대한 Cu(II), Ni(II) 및 Co(II) 착물의 분광학, 열 및 생물학적 연구)

  • Refat, Moamen S.;Megahed, Adel S.;El-Deen, Ibrahim M.;Grabchev, Ivo;El-Ghol, Samir
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.28-37
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    • 2011
  • Spectroscopic (infrared, electronic and $1^H$-NMR), elemental analyses CHN, molar conductivity, thermogravimetric analyses (TGA/DTG) and biological studies, of both benzanthrone derivatives 3-N-2-hydroxy ethylamine benzanthrone (HEAB) and 3-N-2-amino ethylamine benzanthrone (AEAB) with Cu(II), Co(II) and Ni(II) chlorides were discussed herein. Based on the above studies, HEAB ligand was suggested to be coordinated to each metal ions via hydroxo and amino groups to form [Cu(HEAB)$(Cl)_2$].$2H_2O$, [Co(HEAB)$(Cl)_2(H_2O)_2$].$8H_2O$ and [Ni(HEAB)$(Cl)_2(H_2O)_2$].$7H_2O$ coordinated complex. On the other hand, AEAB has an octahedral coordinated feature with formulas [Cu(AEAB)$(Cl)_2(H_2O)_2$].$2H_2O$, [Co(AEAB)$(Cl)_2(H_2O)_2$].$4H_2O$ and [Ni(AEAB)$(Cl)_2(H_2O)_2$]. $6H_2O$. The molar conductance values at $25{\circ}C$ for all complexes in DMF are slightly higher than free ligands; this supported the presence of chloride ions inside the coordination sphere. Both benzanthrone ligands and their complexes have been screened against different kinds of bacteria.

The Effect of Ligand's Spin-Orbit Coupling and the Intermixing of │3d 〉 and │4p 〉 Cu Atomic Orbitals on Zero-Field Splitting in the Tetragonally Distorted Tetrahedral $CuCl_4^{2-}\;Complex^\ast$ (Cu 3d 와 4p 궤도함수의 혼성과 리간드의 Spin-Orbit Coupling 이 Tetragonally 일그러진 $CuCl_4^{2-}$ 착물의 Zero-Field Splitting에 미치는 영향)

  • Lee, Wang No;Choe, U Seong;Baek, U Hyeon;Kim, Dong Hui;Choe, Chang Jin;Lee, Gi Gye
    • Journal of the Korean Chemical Society
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    • v.34 no.1
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    • pp.37-43
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    • 1990
  • An effect of the spin-orbit coupling interaction of ligand orbitals and the intermixing │3d 〉and│4p > transition metal atomic orbitals on the ground state for a 3$d^9$ system in a strong crystal field of tetragonally distorted tetrahedral symmetry that belongs to the $D_{2d}$ point group has been investigated in this work, applying the degenerate perturbation theory. An LCAO-MO analysis in terms of the known energies of the d-d transitions for the tetragonally distorted $CuCl_4^{2-}$ ion in a single crystal of$Cs_2CuCl_4$shows that the covalent mixing of Cu 3d and ligand Cl 3p orbitals decreases dramatically with increasing Cu 4p contribution. The extent of effect on the energy level splitting for the ground state by the spin-orbit coupling interaction of ligand orbitals decreases significantly in orderTEX>$\Gamma_7(E)\;\to\;\Gamma_6(E)\; >\;\Gamma_7(B_2)\;\to\;\Gamma_6(E)\; >\;\Gamma_7(B_2)\;\to\;\Gamma_7(E)$.

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