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Molybdenum(Ⅴ)-Oxo Complexes with Oxygen, Nitrogen and Sulfur Donors. Synthesis, Spectral and Electrochemical Properties (산소, 질소, 그리고 황 주개 원자의 몰리브덴(Ⅴ)-산소 착물 합성과 분광학적 및 전기화학적 성질)

  • Kim, Hee-Jung;Koo, Bon-Kweon
    • Journal of the Korean Chemical Society
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    • v.39 no.6
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    • pp.434-439
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    • 1995
  • Six-coordinate molybdenum(Ⅴ)-oxo complexes, (R4N)[MoO(NCS)2L](R=CH3, C2H5, n-C4, H9) with S-methyl-3-(2-hydroxy-x-phenyl)methylenedithiocarbazate(L1: x=5-H) and its derivatives (L2:x=5-CH3, L3: x=3-CH3O, L4: x=5,6-C4H4 and L5: x=5-NO2) have been synthesized and the structural, spectral and electrochemical properties of the complexes have been characterized by elemental analysis, molar conductivity, UV-Vis, IR, 1H NMR, and CV (cyclic voltammetry).

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Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

Synthesis and Characterization of Air Stable σ-Bonded ortho-carborane Manganese Metal Complexes $1-[Mn(CO)_5]-2-R-1,2-closo-(σ-C_2B_{10}H_{10}$ and Their Conversion to the Stable ortho-carborane Substituted Fischer-type Carbene Compexes 1-[(CO

  • 김세진;김유혁;고재정;강상욱
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.634-641
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    • 1995
  • The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

Synthesis and Spectroscopic Investigations of Some New rganotelluronium alts Based on Dicyclohexyl Telluride (디시클로헥실 텔루르염에 기반한 유기텔루로늄염의 성과 분광학적 분석)

  • Al-Rubaie, Ali Z.;Al-Mudhaffar, Dhafir M. H.;Al-Mowali, Ali H.;Asker, Kahtan A.
    • Journal of the Korean Chemical Society
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    • v.53 no.5
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    • pp.530-535
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    • 2009
  • Dicyclohexyl telluride was obtained in a high yield by the reaction of cyclohexyl bromide with NaTeH(prepared in situ) in an aqueous ethanolic solution. A series of new organotelluronium salts of the general formula ${(cyclo-C_6H_11)}_2Te(R)X$ (where R = $CH_3$, X = I (1); R = $C_2H_5$, X = Br(2); R = $C_2H_5$, X = I (3); R = C_3H_5$, X = Br (4)) were prepared by the reaction of ${(cyclo-C_6H_11)}_2Te$ with the corresponding alkyl halide. Reaction of 1 with NaBPh4 gave compound 5 ( i.e. R = CH3, X = BPh4 ‒) in 78% yield. Reaction of ${(cyclo-C_6H_11)}_2Te$ with benzyl bromide and 4-bromophenacyl bromide gave unexpectedly dibenzylcyclohexyltelluronium bromide (6) and bis(4-bromophenacyl)cyclohexyltelluronium bromide (7), respectively. Reaction of 6 with NaBPh4 gave the corresponding tetraphenylborate derivative (8) in high yield. $^1H$ NMR studies revealed that in $CDCl_3$solution compound 1 eliminated alkyl halide. Conductivity, IR, $^1H\;and\;^{13}C$ NMR and thermal data for the new compounds are presented and discussed.

Synthesis and Sintering of Cordierite by using Coprecipitation Method (공침법에 의한 Cordierite분말의 합성 및 소결에 관한 연구)

  • 한문희;박금철
    • Journal of the Korean Ceramic Society
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    • v.27 no.7
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    • pp.899-906
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    • 1990
  • The cordierite powders were prepared from Mg(NO3)2.6H2O, Al(NO3)3.9H2O and colloidal silica by the coprecippitation method, and the sintering behavior of the powders were investigated. Two different methods were applied for producing the precursor powders. The one was to added the aqueous solution of Mg(NO3)2.6H2O and Al(NO3)3.9H2O to NH4OH to adjust pH at 10 where the colloidal silica of pH 10 was added. The other wa to add the aqueous solution of Mg(NO3)2.6H2O and Al(NO3)3.9H2O to the colloidal silica with NH4OH to control the final mixture to be at pH 10. It was confirmed that more homogeneous powders were obtained from the latter method. The firing linear shrinkage of the powder compacts fabricated from the calcined powder between 90$0^{\circ}C$ and 110$0^{\circ}C$ was found to be larger as the calcination temperature was low. But all of them stopped shrinking around 120$0^{\circ}C$. The powder compacts, fabricated using the calcined powders at 90$0^{\circ}C$ and 95$0^{\circ}C$ for 2hours and sintered at 142$0^{\circ}C$ for 2hours, showed relative density of 93-96%, 3-point bending strength of 81-83MPa, KIC of 1.9-2.4 MPam1/2 and thermal expansion coefficient of 0.213-0.732$\times$10-6$^{\circ}C$.

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Reactions, Hydrogenation and Isomerization of Unsaturated Esters with a Rhodium(I)-Perchlorato Complex

  • Jeong Hyun Mok;Chin Chong Shik
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.468-471
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    • 1986
  • The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

Synthesis and Characterization of Pd(II) Complexes with Adenine, Uracil, Cytosine and Malonate Ligands (아데닌, 우라실, 시토신 및 말로네이트 배위자를 가진 팔라듐(II) 착물의 합성과 그 성질)

  • Sang-Oh Oh;Sung-Jong Mo
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.320-326
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    • 1986
  • The antitumor properities of metal are not limited to Pt(II) complexes. Recently, it was reported that some Pt(II) and Pd(II) complexes with sulfur and nitrogen ligands had potential antitumor reactivity. Pt(II) complexes is toxic drug for anticancer. Therefore, the complexes of Pd(II) with adenine, uracil, cytosine and malonate ligands are interesting for anticancer drug. We synthesized new palladium complexes containing nucleosides. The reactions of Pd(II) with adenine, uracil, cytosine and malonate ligands have been studied in aqueous solutions. The complexes isolated from these reactions have the following formulas; $[Pd(en)(C_5H_5N_5)_2](NO_3)_2,\;[Pd(en)(C_4H_3N_2O_2)Cl],\;[Pd(en)(C_3H_2O_4)]\;and\;[Pd(en)(C_4H_5N_3O)_2](NO_3)_2{\cdot}(C_4H_5N_3O)$. The compounds have been identified by elemental analysis, mass spectra, infrared spectra and electronic spectra.

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Effects of Heat Treatment Conditions of FeC2O4·2H2O on the Formation of Fe3O4-δ (FeC2O4·2H2O의 열처리 조건이 Fe3O4-δ 형성에 미치는 영향)

  • Oh, Kyoung-Hwan;Park, Won-Shik;Rhee, Sang-In;Suhr, Dong-Soo
    • Korean Journal of Materials Research
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    • v.22 no.11
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    • pp.620-625
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    • 2012
  • A general synthetic method to make $Fe_3O_{4-{\delta}}$ (activated magnetite) is the reduction of $Fe_3O_4$ by $H_2$ atmosphere. However, this process has an explosion risk. Therefore, we studied the process of synthesis of $Fe_3O_{4-{\delta}}$ depending on heat-treatment conditions using $FeC_2O_4{\cdot}2H_2O$ in Ar atmosphere. The thermal decomposition characteristics of $FeC_2O_4{\cdot}2H_2O$ and the ${\delta}$-value of $Fe_3O_{4-{\delta}}$ were analyzed with TG/DTA in Ar atmosphere. ${\beta}-FeC_2O_4{\cdot}2H_2O$ was synthesized by precipitation method using $FeSO_4{\cdot}7H_2O$ and $(NH_4)_2C_2O_4{\cdot}H_2O$. The concentration of the solution was 0.1 M and the equivalent ratio was 1.0. ${\beta}-FeC_2O_4{\cdot}2H_2O$ was decomposed to $H_2O$ and $FeC_2O$4 from $150^{\circ}C$ to $200^{\circ}C$. $FeC_2O4$ was decomposed to CO, $CO_2$, and $Fe_3O_4$ from $200^{\circ}C$ to $250^{\circ}C$. Single phase $Fe_3O_4$ was formed by the decomposition of ${\beta}-FeC_2O_4{\cdot}2H_2O$ in Ar atmosphere. However, $Fe_3C$, Fe and $Fe_4N$ were formed as minor phases when ${\beta}-FeC_2O_4{\cdot}2H_2O$ was decomposed in $N_2$ atmosphere. Then, $Fe_3O_4$ was reduced to $Fe_3O_{4-{\delta}}$ by decomposion of CO. The reduction of $Fe_3O_4$ to $Fe_3O_{4-{\delta}}$ progressed from $320^{\circ}C$ to $400^{\circ}C$; the reaction was exothermic. The degree of exothermal reaction was varied with heat treatment temperature, heating rate, Ar flow rate, and holding time. The ${\delta}$-value of $Fe_3O_{4-{\delta}}$ was greatly influenced by the heat treatment temperature and the heating rate. However, Ar flow rate and holding time had a minor effect on ${\delta}$-value.

Micro Structure and the Coefficient of Friction with $H_2S$ and $C_3H_8$ Gas Addition During Plasma Sulf-nitriding of SM45C Carbon Steel (SM45C 탄소강의 플라즈마 침류질화 처리 시 $H_2S$, $C_3H_8$ 가스 첨가에 따른 미세조직 및 마찰계수의 변화)

  • Ko, Y.K.;Moon, K.I.;Lee, W.B.;Kim, S.W.;You, Y.Z.
    • Journal of the Korean Society for Heat Treatment
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    • v.20 no.5
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    • pp.237-242
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    • 2007
  • Friction coefficient of SM45C steel was surprisingly reduced with $H_2S$ and $C_3H_8$ gas during plasma sulf-nitriding. During the plasma sulf-nitriding, 100-700 sccm of $H_2S$ gas and 100 sccm of $C_3H_8$ gas were added and working pressure and temperature were 2 torr, $500-550^{\circ}C$, respectively. As $H_2S$ gas amount increased over 500 sccm, flake-like structures were developed on top of the nitriding layer and grain size of the nitriding layer were about 100 nm. The friction coefficient for the sample treated plasma sulf-nitriding under $N_2-H_2S$ gas was 0.4 - 0.5. The structure became more finer and amorphous-like along with $N_2-H_2S-C_3H_8$ gas and the nano-sized surface microstructures resulted in high hardness and significantly low friction coefficient of 0.2.

Performance Characteristics of New LNG Liquefaction Cycles with Temperature Differences in the Heat Exchangers (열교환기 온도차에 따른 새로운 LNG 액화사이클의 성능 특성)

  • Yoon, Jung-In;Son, Chang-Hyo
    • Journal of Power System Engineering
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    • v.18 no.1
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    • pp.51-56
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    • 2014
  • In this paper, the performance of the $CO_2-C_2H_6-N_2$ cascade liquefaction cycle with respect to temperature differences in the LNG heat exchangers is analyzed theoretically using HYSYS software and then compared the COP(coefficient of performance) of the cascade liquefaction cycles using $C_3H_8-C_2H_4-C_1H_4$ and $CO_2-N_2O-N_2$. In comparison of COP of three cycles, the cascade liquefaction cycles using $C_3H_8-C_2H_4-C_1H_4$ showed the highest COP. And the liquefaction cycle using $CO_2-C_2H_6-N_2$ and $CO_2-N_2O-N_2$ presented the second and third highest COP, respectively. In case of COP, the $C_3H_8-C_2H_4-C_1H_4$ cascade liquefaction cycle yields better COP. But, in terms of the environment and maintain, it is confirmed that the cascade liquefaction cycle using $CO_2-C_2H_6-N_2$ provides favorable characteristics.