• Title/Summary/Keyword: triphenylphosphine

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Hydrodediazoniation of Arenediazonium Tetrafluoroborate with Triethylamine

  • 박군하;조윤환;장은주
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.179-182
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    • 1996
  • Hydrodediazoniation product (3a-d) was found to be the major product in the reaction of arenediazonium tetrafluoroborate (1a-d) with triethylamine (2) in methanol under nitrogen at room temperature. A quantitative study on the title reaction was investigated in detail and two remarks were noteworthy. One was the linear increase in the yield of 3a-d by increasing the molar concentration of 2 until equimolar concentration was reached between 1a-d and 2. The other was the suppression of the formation of 3a-d in the presence of oxygen. Based on these results, the title reaction was better understood by 1:1 electron transfer reaction between reactants (1a-d and 2) rather than by radical chain mechanism proposed in the reaction of arenediazonium tetrafluoroborate and triphenylphosphine.

Evidence for Nitrogen-Bonded Acrylonitrile to Iridium (Ⅰ) in Acrylonitrilecarbonylbis(triphenylphosphine)iridium (Ⅰ) perchlorate

  • Park, Soon-Heum;Park, Hwa-Kun;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.5 no.4
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    • pp.167-169
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    • 1984
  • Analyses of $_1$H-NMR, infrared and electronic spectral data for $[Ir(CH_2 = CHCN)(CO)(P(C_6H_5)_3)_2]ClO_4 (1)$prepared by the reaction of $Ir(OClO_3)(CO)(P(C_6H_5)_3)_2$ with $CH_2 = CHCN$, agree with the suggestion that 1 is a mixture of the nitrogen-bonded acrylonitrile complex, $[(CO)(P(C_6H_5)_3)_2Ir-NCCH = CH_2]ClO_4$ and other compound which may be the C = C ${\Pi}$ -system-bonded acrylonitrile complex, "[(CO)(P(C6H5)3)2Ir-CHCN = CH2]ClO4.

Homogeneous Catalysis (IV). Hydrogenation of Acrylonitrile with trans-Chlorocarbonylbis(triphenylphosphine)rhodium(I)

  • Woo, Jin-Chun;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.4 no.4
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    • pp.169-171
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    • 1983
  • It has been found that the acrylonitrile solution of trans-$RhCl(CO)(Ph_3P)_2$ produces propionitrile catalytically at $90^{\circ}C$ under $P_{H_2}$=3 atm. This catalytic hydrogenation proceeds only for a certain period of time producing ca. 50 moles of propionitrile per mole of the rhodium complex. The hydrogenation with trans-$RhCl(CO)(Ph_3P)_2$ in the presence of formaldehyde is much faster than in the absence of formaldehyde, and continues without a decrease in the rate for a prolonged period of time. It is suggested that the hydrogenation with trans-$RhCl(CO)(Ph_3P)_2$ proceeds through the unsaturated route initiated by the dissociation of CO from trans- $RhCl(CO)(Ph_3P)_2$ to give coordinatively unsaturated $RhCl(Ph_3P)_2$.

Synthesis and Characterization of Molybdenum(Ⅲ) and (Ⅳ) Complexes with N, P, O-Donating Ligands(Ⅲ) (질소, 산소, 인 주개 리간드를 갖는 몰리브덴 (Ⅲ) 및 (Ⅳ) 착물의 합성과 특성 (제 3 보))

  • Kim, Eun Gi;Yu, Eun Yeong;Park, Yu Cheol
    • Journal of the Korean Chemical Society
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    • v.38 no.2
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    • pp.101-107
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    • 1994
  • Some molybdenum(III) and (IV) complexes have been prepared from the reaction of $MoCl_4$·2MeCN with N, P, O-donating ligands and characterized by elemental analysis, infrared and UV-Visible spectroscopy. 3,5-Lutidine, 1,2-phenylenediamine, 8-hydroxyquinoline, 9,10-phenanthrenequinone, triphenylphosphine and 1,2-bis(diphenylphosphino)ethane were chosen as coordinating ligands. Stretching frequencies $\upsilon$ (Mo-Cl) of Mo(IV) appear at higher frequencies than those of Mo(III) complexes due to the increasing oxidation number of metal. $MoCl_4(L)_2$ exhibit one Mo-Cl stretching frequency, whereas Mo$Cl_4$(L^L) exhibit four Mo-Cl stretching frequencies. The number of Mo-Cl stretching frequency suggestes the former complexes have trans($D_{4h}$) and the latter complexes have cis($C_{2v}$) symmetry. Stretching frequency ${\nu}g(C{\equiv}N)$ of acetonitrile in Mo(III) complexes are shifted to about 30 $cm^{-1}$ higher frequency compared with that of a free ligand (2260 $cm^{-1}$). These spectral data indicates that Mo(III) complexes are in the octahedral geometries with the coordinated acetonitrile. Finally each molybdenum(III) and (IV) complexes showed the following formulation; $[MoCl_4(L)_2]$,[Mo$Cl_4$(L^L)], $[MoCl_3(L)_2MeCN]$ and [Mo$Cl_3$(L^L)MeCN].

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Synthesis and Characterization of Vanadium(Ⅲ) Complexes with N, P, O-donating Ligands(Ⅱ) (질소, 산소, 인 주개 리간드를 갖는 바나듐(Ⅲ) 착물의 합성과 특성 (제 2 보))

  • Oh Sang-Oh;Lyou Eun-Young
    • Journal of the Korean Chemical Society
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    • v.37 no.6
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    • pp.612-617
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    • 1993
  • Some vanadium(III) complexes have been prepared from the reaction of VC$l_3$ with N, P, O-donating ligands and characterized by elemental analysis, $^1$H-NMR infrared and UV-Visible spectroscopy. 3,5-Lutidine, 1,2-phenylenediamine, 8-hydroxyquinoline, 9,10-phenanthrenequinone, triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene were chosen as coordinating ligands. Stretching frequency ${\nu}g$(V-Cl) of complexes appears) at 298∼367 cm-1, which show octahedral geometries. Stretching frequency of ${\nu}g$(V-X) (X = N, P, O) indicates that ligands are coordinated to vanadium(III). Stretching frequency ${\nu}g(C{\equiv}N)$ of acetonitrile in these complexes are characteristically shifted to about 70 c$m^{-1}$ higher compared with that of a free ligand (2260 c$m^{-1}$). Bending frequency of $\delta(C{\equiv}N)$ is also shifted to about 60 c$m^{-1}$ higher compared with that of a free ligand (377 c$m^{-1}$). Finally each vanadium(III) complex showed the following formulation; [VC$l_3$(L)$_2$MeCN] or [VC$l_3$(L-L)MeCN].

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Ligand Effect in Recycled CNT-Pd Heterogeneous Catalyst for Decarboxylative Coupling Reactions

  • Kim, Ji Dang;Pyo, Ayoung;Park, Kyungho;Kim, Gwui Cheol;Lee, Sunwoo;Choi, Hyun Chul
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2099-2104
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    • 2013
  • We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

Characteristics of Recycled m-Aramid and TPP Complex Solutions in Preparation and Cotton Fibers after Coating (재활용 메타 아라미드와 TPP 복합용액의 제조 및 면섬유 코팅 후 특성분석)

  • Kim, Sam Soo;Lee, Ji Min;Cho, Ho Hyun;Ryoo, Kyu Yul
    • Textile Coloration and Finishing
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    • v.25 no.4
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    • pp.292-302
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    • 2013
  • Cotton fabrics treated with hybrid materials were developed and prepared. A halogen-free flame retardant and an aromatic amide were blended and applied to cotton fabrics. Thermal and physical properties of the treated cotton fabrics were investigated. The surface of the pure and coated cotton fabrics was characterized by Fourier transform infrared spectroscopy. The elemental composition of the coated surface of the cotton fabric was measured using X-ray photoelectron spectroscopy and compared with that of pure cotton fabric. After being solved in N,N-dimethylacetamide, m-aramid and triphenylphosphine oxide (TPP) were applied to cotton fabrics through a dip-pad-coagulation process. The treated cotton fabrics with recycled m-aramid/TPP resulted in increased limited oxygen index values and thermal resistance.

Electrical Conduction and Emission Properties of (tb-PMP)3Tb-(Ph3PO) Single Layer OLEDs ((tb-PMP)3Tb-(Ph3PO) 단일층 OLEDs의 전기전도 및 발광 특성)

  • Moon, Dae-Gyu
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.19 no.9
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    • pp.878-882
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    • 2006
  • We have fabricated single organic layer devices of the organolanthanide complex, terbium tris-(1-phenyl-3-methyl-4-(tertiarybutyry)pyrazol-5-one)triphenylphosphine oxide [$(tb-PMP)_{3}Tb-(Ph_{3}PO)$] for the investigation of its light emission and electrical conduction properties. The thickness of ($(tb-PMP)_{3}Tb-(Ph_{3}PO)$) layer was varied to 60, 75, 95 nm. Mg and Ca layers were used for the cathode contact. The electrical conduction in the $(tb-PMP)_{3}Tb-(Ph_{3}PO)$ single layer devices was dominated by the injection of electrons into the organic layer from the cathode. A higher current density at much lower voltages can be attained with Ca cathode because of the enhanced electron injection. The device shows very sharp emission at 548 nm. The FWHM of the strongest emission peak was 12 nm.

Effect of Curing Agent on the Curing Behavior and Joint Strength of Epoxy Adhesive (에폭시 접착제의 경화거동 및 접합강도에 미치는 경화촉매제의 영향)

  • Kim, Min-Su;Kim, Hae-Yeon;Yoo, Se-Hoon;Kim, Jong-Hoon;Kim, Jun-Ki
    • Journal of Welding and Joining
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    • v.29 no.4
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    • pp.54-60
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    • 2011
  • Adhesive bonding is one of the most promising joining methods which may substitute for conventional metallurgical joining processes, such as welding, brazing and soldering. Curing behavior and mechanical properties of adhesive joint are largely dependent on the curing agent including hardener and catalyst. In this study, effects of curing system on the curing behavior and single-lap shear strength of epoxy adhesive joint are investigated. Dihydrazide, anhydride and dicyandiamide(DICY) were chosen as hardener and imidazole and triphenylphosphine(TPP) were chosen as catalyst. In curing behavior, TPP showed the delay of the curing rate for DICY and ADH at $160^{\circ}C$, compared to imidazole catalyst due to the high curing onset/peak temperature. DICY seemed to be most beneficial in the joint strength for both steel and Al adherends, although the type of adherends affected the shear strength of epoxy adhesive joint.

Synthesis and Catalytic Activity of Water-Soluble Iridium-Sulfonated Triphenylphosphine Com;lex. Hydration of Nitriles

  • 진종식;김상열;주광석;원경식;종대성
    • Bulletin of the Korean Chemical Society
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    • v.20 no.5
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    • pp.535-538
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    • 1999
  • Five coordinated water-soluble iridium(l) complex, IrH(CO)(TPPTS)3 (1) (TPPTS = P(m-C6H4SO3Na)3-xH2O) has been prepared from the reaction of IrCl3·3H2O with TPPTS and HCHO in H2O/EtOH solution. Complex 1 catalyzes the hydration of nitrites (RC ≡ N, R = CH3, CICH2, CH3(CH2)4, Ph) in aqueous solution to give the corresponding amides (RCONH2) at 100℃. The hydration of unsaturated nitrites (R'C ≡ N, R'=CH3CH=CH, CH3OCH=CH, trans-PhCH=CH, CH2=C(CH3)) takes place regioselectively on-C ≡ N group to give unsaturated amides (R'CONH2) leaving the olefinic group intact. The yields of the amides seem to be depending on the electrophilicity of the carbon of nitrile: The more the electron withdrawing ability of the substituents on nitrites, the more amides are obtained. The hydration of dinitriles (NC-R-CN, R=(CH2)4, (CH2)6) with complex 1 initially gives mono-hydration products (NC-R-CONH2) which are slowly hydrated further to give dihydration products (H2NCO-R-CONH2). The hydration of 1,4-dicyanobutane has been found to be somewhat faster than that of 1,6-dicyanohexane.