• Title/Summary/Keyword: C2H

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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.

DFT Study for Substitution Patterns of C20H18X2 Regioisomers (X = F, Cl, Br, or OH)

  • Hwang, Yong-Gyoo;Lee, Seol;Lee, Kee-H.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.641-646
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    • 2012
  • We used the hybrid density-functional (B3LYP/6-31G(d,p)) method to analyze the substitution patterns of $C_{20}H_{18}X_2$ derivatives (X = F, Cl, Br, or OH) obtained as disubstituted $C_{20}H_{20}$ cages. Our results suggest that the cis-1 regioisomers (1,2-dihalo derivatives) are less stable than the trans-1 regioisomers (1,20-dihalo derivatives), whereas in the case of the dihydroxy derivatives, the cis-1 regioisomer is more stable than the trans-1 regioisomer. This implies that in the dihalo-induced strain cages of $C_{20}H_{18}X_2$, the strain effect would affect the relative energies, while in the dihydroxide, the hydrogen bonds have a stronger effect on the relative energies in cis-1 regioisomer than the strain effect do. Thus this supports the experimental result in which the bisvicinal tetrol was of particular preparative-synthetic interest as a substitute for the lacking bisvicinal tetrabromide. Further, the topologies of the HOMO and LUMO characteristics of all $C_{20}H_{18}Cl_2$ and $C_{20}H_{18}Br_2$ regioisomers with the same symmetry are same, but they are different from those of $C_{20}H_{18}F_2$ and $C_{20}H_{18}(OH)_2$. This indicates that the five regioisomers of each $C_{20}H_{20}$ disubstituted derivative will have an entirely different set of characteristic chemical reactions.

Electrical characteristics of 4H-SiC MIS Capacitors With Ni/CNT/SiO2 Structure (Ni/CNT/SiO2 구조의 4H-SiC MIS 캐패시터의 전기적 특성)

  • Lee, Taeseop;Koo, Sang-Mo
    • Journal of IKEEE
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    • v.18 no.4
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    • pp.620-624
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    • 2014
  • In this study, the electrical characteristics of Ni/CNT/$SiO_2$ structures were investigated in order to analyze the mechanism of carbon nanotubes in 4H-SiC MIS device structures. We fabricated 4H-SiC MIS capacitors with or without carbon nanotubes. Carbon nanotubes were dispersed by isopropyl alcohol. The capacitance-voltage (C-V) is characterized at 300 to 500K. The experimental flat-band voltage ($V_{FB}$) shift was positive. Near-interface trapped charge density and oxide trapped charge density values of Ni/CNT/$SiO_2$ structure were less than values of reference samples. With increasing temperature, the flat-band voltage was negative. It has been found that its oxide quality is related to charge carriers or defect states in the interface of 4H-SiC MIS capacitors. Gate characteristics of 4H-SiC MIS capacitors can be controlled by carbon nanotubes between Ni and $SiO_2$.

Separation of $C_3H_6/C_3H_8$ by PEBAX-NaY Zeolite Composite Membranes (PEBAX-NaY Zeolite 복합막에 의한 $C_3H_6/C_3H_8$ 분리에 관한 연구)

  • Kim, Seul-Gi;Lee, Hyun-Kyung
    • Membrane Journal
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    • v.25 no.1
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    • pp.42-47
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    • 2015
  • In this study, PEBAX[poly(ether-block-amide)]-NaY zeolite composite membranes were prepared, and those prepared membranes were studied on permeability of $C_3H_6$ and $C_3H_8$, and selectivity ($C_3H_6/C_3H_8$). NaY zeolite particles in PEBAX-NaY zeolite composite membranes was dispersed as aggregated particles with the size $0.5{\sim}2.5{\mu}m$ by SEM observation. TGA measurement showed the weight loss change resulted from the amount of NaY zeolite when NaY zeolite was added into PEBAX. By gas permeation experiment, the permeabilities of $C_3H_6$ and $C_3H_8$ were decreased by the more addition NaY zeolite in PEBAX. Overall, $C_3H_6$ was having higher permeability than $C_3H_8$. The selectivity $C_3H_6/C_3H_8$ was decreased by the more NaY zeolite in PEBAX.

Studies on the Molybdenum Complexes with Tetradentate Schiff Base Ligand (I). N,N'-bis (Salicylaldehyde)-ethylene Diimine (네자리 Schiff Base 리간드의 몰리브덴착물에 관한 연구 (제1보))

  • Jo, Gi Hyeong
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.267-271
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    • 1974
  • The tetradentate schiff base, N,N'-bis(salicylaldehyde)-ethylene diimine has been reacted with a series of Mo(IV), Mo(V), Mo(IV), and Mo(III) oxidation states to form new Complexes; $[MoO_2(C_{16}H_{14}O_2N_2)], (MoO(C_{16}H_{14}O_2N_2)]_2O, (Mo(SCN)(C_{16}H_{14}O_2N_2)]_2O, and (Mo(H_2O)(C_{16}H_{14}O_2N_2)]_2O.$ These complexes have hexa coordinated configurations and the mole ratio of these ions to the ligand was 1:1. These complexes have been identified by visible spectra, infrared specra, T.G.A., D.T.A., and elemental analysis.

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Synthesis and Characterization of Group 13 Compounds of 2-Acetylpyridine Thiosemicarbazone. Single-Crystal Structure of $(iC_4H_9)-2Al(NC_5H_4C(CH_3)$NNC(S)NHPh)

  • 강영진;강상옥;고재정;손정인
    • Bulletin of the Korean Chemical Society
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    • v.20 no.1
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    • pp.65-68
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    • 1999
  • Novel mononuclear group 13 metal complexes with the formula (R2M){NC5H4C(CH3)NNC(S)NH(C6H5)} (M=Al, R=iC4H9 (1); M=Ga, R=iC4H9 (2); M=Al, R=CH2SiMe3 (3); M=Ga, R=CH2SiMe3 (4)) result when 2-acetyl pyridine 4-phenyl-thiosemicarbazone ligand is mixed with trialkyl aluminum or trialkylgallium. These compounds 1-4 are characterized by microanalysis, NMR (1H, 13C) spectroscopy, mass spectra, and singlecrystal X-ray diffraction. X-ray single-crystal diffraction analysis reveals that 1 is mononuclear metal compound with coordination number of 5 and N, N, S-coordination mode.

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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Study of Complexes of C2- and C6-dihydroceramides with Transition Metal Ions Using Electrospray Ionization Tandem Mass Spectrometry (ESI-MS/MS)

  • Lim, Jin-Yi;Kumar, Avvaru Praveen;Kim, Chang-Dae;Ahn, Chul-Jin;Yoo, Young-Jae;Lee, Yong-Ill
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.397-401
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    • 2009
  • The complexes of $C_2-\;and\;C_6$-dihydroceramides with transition metal ions have been investigated by using Electrospray ionization-tandem mass spectrometry (ESI-MS/MS). The formation and fragmentation pathways of several doubly charged cluster ions as well as singly charged cluster ions of $C_2-\;and\;C_6$-dihydroceramides with transition metal ions have studied by ESI-MS/MS in the positive mode. Under ESI conditions, dihydroceramides form singly and doubly charged complexes with transition metal ions $(Mn^{2+},\;Fe^{2+},\;Co^{2+},\;Ni^{2+},\;and\;Zn^{2+}\;except\;Cu^{2+})$ with the compositions of $[DHCer+M+2H^2O-H]^+,\;[2DHCer+M+2H2O-H]^+,\;[3DHCer+M+2H2O-H]^+,\;[2DHCer+M]^{2+},\;[3DHCer+M]^{2+},\;[4DHCer+M]^{2+},\;[5DHCer+M]^{2+},\;and\;[6DHCer+M]^{2+}\;(DHCer\;=\;C_2-\;or\;C_6$-dihydroceramide, M = transition metal ion). The different complexation behavior of copper is responsible for relatively lower affinity of dihydroceramides to copper compared to those of other transition metals. It is also found that in the mass spectrum of the dihydroceramide complexes with copper(II), [2DHCer+Cu-H]$^+$ was observed with considerable intensity as well as [2DHCer+Cu+2$H_2O-H]^+$ due to its different geometry from those of other metals.

New Transition Metal Mediated Alkylation Reaction of arachno-$S_{2}B_{7}H_{8}$, Insertion Reaction of arachno-$S_{2}B_{7}H_{8}^{-}$ with $(CO)_{5}M$ {${C(R_{1})(R_{2})}$} $(M=Cr,\;W;\;R_{1}=CH_{3},\;C_{6}H_{5};\;R_{2}=OCH_{3},\;SC_{6}H{5})$: Synthesis and Characterization of arachno-$4-RCH_{2}-6,8-S_{2}B_{7}H_{8}\;(R=CH_{3},\;IIa;\;C_{6}H_{5},\;IIb)$

  • Hee-Joo Jeon;Jae-Jung Ko;Kang-bong Lee;Sang Ook Kang
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.113-117
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    • 1993
  • Good yield synthetic routes for the production of new B-alkyl-dithiaborane clusters are reported. The syntheses of the B-alkyl-dithiaboranes are based on the use of Fischer-type carbene reagents to activate the B-H bonds of dithiaborane for alkyl-addition reactions and are the first examples of transition-mediated reactions of dithiaborane to be reported. Thus, reactions employing arachno-$S_2B_7H_8$- and $(CO)_5M{C(R_1)R_2}$ (M = Cr, W; $R_1 = CH_3,\;C_6H_5;\; R_2 = OCH_3,\;SC_6H_5)$ were found to yield the intermidiate anions I, $[(CO)_5M{C(R_1)R_2S_2B_7H_8}]^-$, which upon protonation gave the corresponding neutral, air-sensitive cluster arachno-4-$RCH_2-6,8-S_2B_7H_8(R=CH_3,\;IIa;\;C_6H_5,\;IIb)$ range from 30 to 35% yield. Complexes IIa and IIb are isoelectronic with arachno-6,8-$S_2B_7H_9$ and, on the basis of the spectroscopic data, are proposed to adopt a similar arachno cage geometry in which an $RCH_2$ units are substituted to 4 position boron atom of the arachno-6,8-$S_2B_7H_9$.

Comparison of hydrogenases prepared from Clostridium butyricum and Thiocapsa roseopersicina (Clostridium butyricum [절대혐기발효세균]과 Thiocapsa roseopersicina [홍색유황세균]의 수소생산 효소 특성 비교)

  • Baek, Jin-Sook;Yun, Young-Su;Kim, Mi-Sun
    • Transactions of the Korean hydrogen and new energy society
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    • v.16 no.3
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    • pp.219-228
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    • 2005
  • Fermentative strict anaerobic bacterium, Clostricium butyricum NCIB 9576 (Cl. butyricum) and purple sulfur phototrophic bacterium, Thiocapsa roseopersicina NCIB 8347 (T. roseopersicina) were compared on their temperature and oxygen stabilities of cytoplasmic hydrogenases. Cell growth phase and the specific activities of evolution $H_2ase$ were related for both strains, exhibiting the highest cytoplasmic $H_2ase$ activities during the logarithmic growth phases which were 4 and 18 hrs after the incubation for Cl. butyricum and T. roseopersicina, respectively. The optimum temperatures for the growth of Cl. butyricum and T. roseopersicina were 37$^{\circ}C$ and 27$^{\circ}C$, respectively, while those for $H_2$ evolution of cytoplsmic hydrogenases prepared from Cl. butyricum ($C-H_2ase$) and T. roseopersicina ($T-H_2ase$) were 45$^{\circ}C$ and 65$^{\circ}C$, respectively. $T-H_2ase$ was more thermo-stable than $C-H_2ase$. $T-H_2ase$ retained its full activity for 5 hrs at 50$^{\circ}C$ and retained 90% of its original activity for 5 hrs at 60$^{\circ}C$, however, $C-H_2ase$ lost its activity drastically at 50$^{\circ}C$. The optimum pHs for $H_2$ oxidation of $C-H_2ase$ and $T-H_2ase$ were 9.0 and 7.5 respectively. The both enzymes showed maximum $H_2$ evolution activity at pH 7.0. Under the aerobic condition, 80% of $T-H_2ase$ activity was retained for 10 hrs at 30$^{\circ}C$, and 50% of activity was still remained after 6 days at the same experimental conditions. But the $C-H_2ase$ was labile to oxygen and lost its activity immediately after the exposure to air.