• Title/Summary/Keyword: $MoCl_5$

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Study on Formation and Properties of Dioxomolybdenum Complexes (디옥소몰리브덴 착물의 합성과 그 성질에 대한 연구)

  • Sang-Oh Oh;Bon-Kweon Koo
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.441-448
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    • 1986
  • Dioxobis(sub.-salicylaldiminato) molybdenum (VI) complexes, $MoO_2\;(X-sal-N-R)_2,\;(X=H,\;5-CH_3,\;R=C_6H_5,\;p-F-C_6H_4,\;m-Cl-C_6H_4,p-I-C_6H_4\;and\;p-C_2H_5-C_6H_4)$, have been prepared by reactions of dioxobis(sub.-salicylaldehydato) molybdenum (VI), $MoO_2(X-sal)_2$ with primary amines, in which $MoO_2(X-sal)_2$ complexes were obtained by acidification of a mixture solution of ammonium paramolybdate in water and appropriate salicylaldehyde in methanol. All these complexes show two strong Mo=O stretching imodes in the 900-940$cm^{-1}$ and p.m.r. spectra exhibited only one signal for the azomethine group. These results confirmed that the complexes are six-coordinated octahedron with a $cis-MoO_2$ group and the geometrical configurations of the complexes possess a C2 axis of symmetry. From the mass analyses of the complexes, it found that the composition ratios of $MoO_2$ : ligand are 1 : 2. The charge transfer transition corresponding to N-Mo, and O-Mo occured at 29,000$cm^{-1}$ and 32,000$cm^{-1}$ respectively. Where, the complexes were found to be non-ionic materials by conductivity measurements in dimethylformamide.

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Preparation and Characterization of Dimeric Molybdenum(Ⅴ) Complexes with Bis(hydroxyethyl)dithiocarbamate (Bis(Hydroxyethyl)dithiocarbamate 의 이핵 몰리브덴 (Ⅴ) 착물 합성과 그 성질)

  • Yeh Gyung-Hak;Koo Bon-Kweon
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.452-459
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    • 1990
  • A series of oxo-and sulfido-bridged molybdenum (V) complexes, Mo$_2$O$_4$L$_2$, Mo$_2$O$_3$L$_4$, Mo$_2$O$_2$S$_2$L$_2$, and Mo$_2$OS$_3$L$_2$ [L = bis(hydroxyethyl)dithiocarbamate] have been prepared. The complexes with bridging and terminal oxo groups have been synthesized by the reactions of (PyH)$_2$MoOCl$_5$ or MoCl$_5$ and ligand in water. One of the rest two complexes, in which bridging and terminal oxo groups have been replaced by sulfido in Mo$_2$O$_4^{2+}$ core, Mo$_2$O$_2$S$_2$L$_2$ have been prepared by addition of triphenylphosphine to a chloroform solution of Mo$_2$OS$_3$L$_2$. While, Mo$_2$OS$_3$L$_2$ is obtained from aqueous solution of (NH$_4$)$_2$MoS$_4$ and ligand in the presence of sodium dithionite. The complexes are identified by elemental analysis, and spectral data of IR, UV-vis, nmr, and mass. Also, the electrochemical behaviour for the complexes in dimethylsulfoxide has been investigated by the cyclic voltammograms.

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고밀도 유도 결합형 플라즈마를 이용한 Mo 건식 식각 특성

  • 성연준;이도행;이용혁;염근영
    • Proceedings of the Korean Vacuum Society Conference
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    • 1999.07a
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    • pp.126-126
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    • 1999
  • 본 실험의 목적은 FED의 상부, 하부 전극으로 사용되는 Mo를 건식, 습식 식각함으로써 DED 소자의 공정을 개발하는 것이다. Mo는 $261^{\circ}C$의 높은 융점을 지니고 있으며, 우수한 열적 안정성과 비교적 낮은 비저항을 가지는 재료로써 FED와 같은 전계 방출 소자의 cathod 팁 및 전극물질로 사용되어지는 가장 보편적인 물질이다. FED와 같은 전계방출소자가 갖추어야 할 요건은 전자 방출 영역이 소자 동작시 변형되지 않아야 하고, 기계적 ,화학적, 열적 내구성이 좋아야 함인데 이러한 요건을 충족시킬 수 있고 가장 범용적으로 사용되는 물질이 Mo이다. 실험에서 사용된 Mo는 DC magnetron sputter를 사용하여 Ar 가스를 첨가하여 5mTorr하에서 Si 기판위에 증착속도를 300$\AA$/min로 하여 1.6$\mu\textrm{m}$ 증착하였다. 본 실험의 Mo 식각은 고밀도 플라즈마원인 ICP를 이용하였다. 식각특성은 식각 가스조합, inductive power, bias voltage, 공정 압력의 다양한 공정 변수에 따른 식각특성 변화를 관찰하였다. 식각시 chlorine 가스를 주요 식각 가스로 사용하고 BCl3, O2, Ar을 첨가가스로 사용하였으며, inductive power는 300-600, bias voltage는 120-200V 사용하였고 압력은 15-30mTorr, 기판온도는 7$0^{\circ}C$로 유지하였으며 식각마스크로는 electron-beam evaporator로 1$\mu\textrm{m}$ 증착한 SiO2를 patterning하여 사용하였다. 식각속도는 stylus profiler를 이용하여 측정하였으며 식각후 profile은 scanning electron microscopy (SEM)을 통하여 관찰하였다. 실험 결과 순수한 Cl2 BCl3 가스만을 사용한 경우 보다는 Cl2 가스에 O2를 첨가하였을 때 좋은 선택비를 얻었다. 또한, inductive power와 bias voltage, Mo의 식각속도의 적절한 조절을 통해 SiO2에 대한 선택도를 변화시킬 수 있었다. Cl2:O2비를 1:1로 하고 400W/-150V, 20mTorr의 압력, 7$0^{\circ}C$ 기판온도에서 식각시 200$\AA$/min의 Mo 식각속도, SiO2와의 선택비 8:1을 얻을 수 있었다. 또한 실제 FED 소자 구조형성에 적용한 결과 비등방적인 식각형상을 형성할 수 있었다.

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Effect of an Adsorbed Residual Chlorine at Adlineation Sites over Formation of $Pt/HxMoO_3$ (활성점에 흡착된 잔존 chlorine이 $Pt/HxMoO_3$ 생성에 미치는 영향)

  • Jin Gul, Kim;Seong-Soo, Kim
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.5 no.4
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    • pp.282-285
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    • 2004
  • Kinetics of H-spillover over $Pt/MoO_3$ was greatly affected by the amount of residual chlorine differing by calcination temperature. Multifacetted techniques for characterization were dedicated to elucidate the faster reduction of chlorine in the isothermal reduction (ITR) at $50^circ{C}$ after calcination. Reduction of residual chlorine over Platinum resulted in opening the more channel of hydrogen pathway into more $MoO_3$ particles and controlling the kinetics of hydrogen uptake.

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Structure and Reactivity of Alkylchloroformates. MO Theoretical Interpretations on Halide Exchange Reaction (염화 포름산 알킬의 구조와 반응성. 할로겐화 이온 교환반응에 대한 분자궤도론적 고찰)

  • Lee, Bon Su;Lee, Ik Choon
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.223-238
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    • 1974
  • CNDO/2 MO theoretical studies and kinetic studies of halide exchange reactions for alkylchloroformates have been carried out in order to investigate structure-reactivity relationship of alkylchloroformates. From the result of energetics, it was concluded that the most stable configuration of alkylchloroformate is that in which alkyl group and chlorine are trans to each other, and that the hindered rotation about the bond between the carbonyl carbon and alkoxy-oxygen bond is attributed to the ${\pi}-$electron delocalization. It has been found that the large charge separation is due to -M effect of carbonyl and alkoxy oxygens and-I effect of chlorine. The order of rates in solvents studied was $(CH_3)_2 > CO > CH_3CN{\gg}MeOH.$$I^->Br^->Cl^-$ in protic solvent, and of Cl^->Br^- >I^-$ in dipolar aprotic solvents. Alkyl group contribution has the decreasing order of $CH_3-> C_2H-{\gg}i-C_3H_7-.$ The solvent effect has been interpreted on the basis of initial and final state contribution. A transition state model has been suggested, and it has been proposed that the most favorable mechanism is the addition-elimination. From the results of activation parameters and electronic properties, an energy profile has been proposed. Structural factors determining reactivities of alkylchloroformates have been shown to be charge, energy level of ${\alpha}^*LUMO$ to C-Cl bond and ${\alpha}^{\ast} $antibonding strength with respect to C-Cl bond in this MO. Charge and polarizability of nucleophile, and the interaction of these effects with solvent structures are also found to be important.

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Evolution of Hydrothermal Fluids at Daehwa Mo-W Deposit (대화 Mo-W 열수 맥상 광상의 유체 진화 특성)

  • Jo, Jin Hee;Choi, Sang Hoon
    • Economic and Environmental Geology
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    • v.46 no.1
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    • pp.11-19
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    • 2013
  • The Daehwa Mo-W deposit is located within the Gyeonggi massif. Quartz and calcite vein mineralization occurred in the Precambrian gneiss and Jurassic granites. Three main types (Type I: liquid-rich $H_2O$ type, Type II: vapor-rich $H_2O$ type, Type III: $CO_2-H_2O$ type) of fluid inclusions were observed and are classified herein based on their phase relations at room temperature. Within ore shoots, type III fluid inclusions have been classified into four subtypes (type IIIa, IIIb, IIIc and IIId) based on their volume percent of aqueous and carbonaceous ($CO_2$) phase at room temperatures combined with their total homogenization behavior and homogenization behavior of $CO_2$ phase. Homogenization temperatures of primary type I fluid inclusions in the quartz range from $374^{\circ}C$ to $161^{\circ}C$ with salinities between 13.6 and 0.5 equiv. wt.% NaCl. Homogenization temperatures of primary type III fluid inclusions in quartz of main generation, are in the range of $303^{\circ}C$ to $251^{\circ}C$. Clathrate melting temperatures of the type III fluid inclusions were 7.3 to $9.5^{\circ}C$, corresponding to salinities of 5.2 to 1.0 equiv. wt. % NaCl. Melting and homogenization temperatures of $CO_2$ phase of type III fluid inclusions were -57.4 to $-56.6^{\circ}C$ and 29.0 to $30.8^{\circ}C$, respectively. Fluid inclusion data indicate a complex geochemical evolution of hydrothermal fluids. The Daehwa early hydrothermal system is characterized by $H_2O-CO_2$-NaCl fluid at about $400^{\circ}C$. The main mineralization occurred by $CO_2$ immiscibility at temperatures of about 300 to $250^{\circ}C$. At the late base-metal mineralization aqueous fluid formed by mixing with cooler and less saline meteoric groundwater.

Synthesis and Properties of Poly[4,4-bis(acetoxymethyl)-1,6-heptadiyne]

  • Kim, Yun-Hi
    • Bulletin of the Korean Chemical Society
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    • v.18 no.1
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    • pp.66-70
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    • 1997
  • The polymerization of 4, 4-bis(acetoxymethyl)-1, 6-heptadiyne (BAH) was carried out by MoCl5 and WCl6 with various organometallic cocatalysts. MoCl5-based catalysts were more effective than WCl6-based ones for the cyclopolymerization of BAH. Poly(BAH) was characterized to have polymer backbone with conjugated double bond and cyclic structure by IR, UV-visible, and 1H-and 13C NMR spectroscopies. The polymer was stable up to 310 ℃ and 5 % weight loss show up at 350 ℃. The resulting dark violet polymer exhibited good solubility in common organic solvents and could be cast on a glass plate to give film with good mechanical properties. It was found that oxygen permeability (PO2) and permselectivity (PO2/PN2) of the resulting polymer were 15.2 barrer and 2.84, respectively.

Mo 첨가 및 소둔 열처리에 따른 합금 690의 부식 저항성 및 기계적 특성

  • 전유택;박용수;김영식
    • Proceedings of the Korean Nuclear Society Conference
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    • 1995.05b
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    • pp.597-602
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    • 1995
  • 원자력 발전소 증기발생기 전열관 재료인 합금 600의 대체재료로써 설계된 합금 690의 내식성의 향상을 위해서 염소 이온이 다량 포함된 환경에서의 부식 저항성을 크게 향상시킨다고 보고된 Mo을 첨가하여 부식 및 기계적 특성에 미치는 영향을 알아보았다. 미세조직상 Mo를 첨가함에 따라 기지에 미세한 석출물이 석출되어 입자의 미세화를 얻을 수 있었으며 연신율의 감소없이 항복 강도, 인장 강도 및 경도의 향상을 얻을 수 있었다. 공식 저항성은 Mo의 첨가량이 증가함에 따라 부식 속도가 감소하였다. 양극 분극 시험에서도 5$0^{\circ}C$, 3.5wt% NaCl 용액과 0.5N HCl 용액 모두에서 Mo의 함량이 증가할수록 부동태화 전류 밀도 및 임계 부동태화 전류 밀도가 감소하여 전반적으로 현저한 내식성의 향상을 관찰할 수 있었다.

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Studies for Reestabilishment of Approval Toxin Amount in Paralytic Shellfish Poison-Infested Shellfish 5. Comparison of Toxicity and Toxin Composition of Paralytic Shellfish Poison between Blue mussel, Mytilus edulis and Oyster, Crassostrea gigas

  • Shin, Il-Shik;Kim, Young-Man
    • Journal of Food Hygiene and Safety
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    • v.15 no.4
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    • pp.287-292
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    • 2000
  • The toxicity and toxin composition between blue mussel, Mytilus edulis and oyster, Crassostrea gigas collected at Woepori in Ko je island in South Coast of Korea in 1996 and 1997 were compared. The highest toxicity score was about 10 times higher in blue mussel than oyster (blue mussel, 8,670 $\mu\textrm{g}$; oyster, 860$\mu\textrm{g}$ in 1996, blue mussel, 5,657 $\mu\textrm{g}$/100g in 1997). The blue mussel also retained its toxicity for slightly longer period than oyster. In the both shellfish, PSP was composed almost exclusively of C toxicity (Cl and C2, 20~65%) and gonyautoxins (GTXl, 2, 3, and 4, 38~78%). In the early period of toxin accumulation, the ratio of 11$\beta$-epimer toxins (C2, GTX4) whose amount was 25~56 mole% (5th March to 12th April in 1996) and 25~80 mole% (18th March to 7th April in 1997), were higher than that of 11-epimer toxins (Cl, GTX2) whose amount was 41~57 mol%(27th May to 3rd June in 1996) and 25~56 mole% (29th April to 12th May in 1997), became higher than that of 11-epimer toxins. The toxin compositions in the both samples changed on a daily basis, presumably owing to metabolism of the toxin in the bivalves.

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Molecular Orbital Interpretation on Antitumor Activity of trans-Palladium(Ⅱ) Complexes by Geometrical Structure of Ligands (Ⅰ) (리간드의 기하학적 구조에 의한 trans-팔라듐(Ⅱ) 착물의 항암활성에 관한 분자궤도함수론적 해석 (Ⅰ))

  • Song, Young Dae;Park, Byung Kak
    • Journal of the Korean Chemical Society
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    • v.39 no.4
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    • pp.244-251
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    • 1995
  • The palladium(II) complexes(where, [Pd(L)2X2], L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Phisox), and 4-amino, 3,5-dimethylisoxazole(4-ADI); X=Cl, Br] with isoxazole and its derivatives are investigated on antitumor activity by EHMO calculation. It is found that the net charge of the two halogen atoms in trans-isomers are greater than those in cis-ones, indicating that ionic character of Pd-X bond in trans-isomers is greater than that of cis-ones, and so dissociation of Cl- ion is easier than that of Br- ion in aqueous solution in body. Furthermore, it is found that the ${\sigma}MO$ energy of Pd(dx2-y2)-X(px) bond $(E{\sigma}(Pd-X))$ is higher than that of Pd(dx2-y2)-N(px) bond $(E{\sigma}(Pd-N))$ without exception, about all the complexes, and also the $E{\sigma}(Pd-X)$ of trans-isomers is higher than that of cis-isomers. From the above facts, the degree of dissociation in Pd-X bond would be related to antitumor activity. In fact, the linear equation of correlation coefficient 0.96 is fairly established between ${\Delta}E{\sigma}(N-X)(E\sigma(Pd-N)-E{\sigma}(Pd-X))$ and inhibitory activity coefficient, logIA.

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