• Title/Summary/Keyword: 팔라듐(II)

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Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(II) Theoretical Studies on Palladium(0, II) Complexes of Unsaturated Carboxylic Acids (포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 2 보). 불포화카르복실산이 배위된 팔라듐 (0, II) 착물에 관한 이론적 연구)

  • Doh Myung-Ki;Bong-Gon Kim;Maeng-Jun Jung;Young-Dae Song;Byung-Kak Park
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.431-441
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    • 1993
  • The structure and reactivity of ${\pi}$-and metallacycle form in the bis(trimethylphosphine) palladium(0) complexes with acrylic acid, methacrylic acid, crotonic acid(A group) and 3-butenoic acid, 4-pentenoic acid(B group) have been investigated by Molecular Mechanics and Extended Huckel Molecular Orbital method. The calculation shows that A groups with large value of frontier electron density of HOMO and LUMO produce $\pi-complexes$ instead of metallacycle. But B groups with small value of frontier electron density of LUMO, especially 3-butenoic acid, form stable metallacycle. Moreover the methyl-substituted five-membered compared with the six-membered metallacycle is energetically stable conformation.

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Palladium(II) Complexes of Aminophosphines (I). Characterization and Synthesis of $[Pd(L)X_2] with X = Cl^-, Br^-, I^-, NCS^-$ (아미노포스핀류를 포함하는 팔라듐 (II) 착물 (제1보). $[Pd(L)X_2] (X = Cl^-, Br^-, I^-, NCS^-)$의 합성과 성질)

  • Myung-Ki Doh;Bong-Gon Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.4
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    • pp.255-261
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    • 1983
  • Several new $[Pd(L)X_2]$ complexes have been prepared with aminophosphines (L) such as trans-1,2-bis[diphenylphosphino)amino]cyclohexane and 1,2-bis[(diphenylphosphino) amino] propane that contain phosphorus atom as ${\pi}$-electron acceptor, and the bond character of complexes have been investigated by means of infrared and electronic spectroscopy. It was found that thiocyanate ions are N-coordinated possibly due to the steric and electronic influence of the phosphorus atom in aminophosphines that formed seven-membered chelate rings, and that spectrochemical series that is derived from the electronic spectra of the complexes is $NCS^- > Cl^- > Br^- > I^-$

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Theoretical Study on Antitumor Activity of Palladium(II) and Platinum(II) Complexes with Isoxazole and Its Derivatives (이소옥사졸과 그의 유도체들이 배위된 팔라듐(Ⅱ)과 백금(Ⅱ) 착물의 항암활성에 관한 이론적 연구)

  • Kim, Jung-Sung;Song, Young-Dae
    • Journal of the Korean Chemical Society
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    • v.42 no.4
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    • pp.369-377
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    • 1998
  • The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

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Palladium-Catalyzed Carbonylative Homocoupling Reaction of Vinylmercuric Chlorides with Carbon Monoxide (팔라듐 촉매를 이용한 Vinylmercuric-chlorides 의 CO 첨가 호모커플링반응)

  • KimJin-Il 김진일;Kwang-Hyek Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.657-661
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    • 1989
  • Symmetrical divinyl ketone or divinyl ${\alpha}$-diketone was synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylmercuric chlorides with carbon monoxide. In order to find out optimum synthetic reaction conditions, we examined the effect of catalysts, bases, solvents and reaction temperature when (E)-styrylmercuric chloride was used as a typical starting material. The best yield of divinyl ${\alpha}$-diketone was obtained in the reaction using 10 mol% of dichlorobis(triphenyl phosphine)palladium (II) as a catalyst, an equivalent of pyridine as a base, 10 mol% of iodine and acetonitrile at 50${\circ}$C under 10 atmospheric pressure of carbon monoxide. The yield of divinyl ${\alpha}$-diketone was decreased under atmospheric pressure of carbon monoxide.

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Palladium Catalyzed New Synthesis of Divinyl Ketones and Divinyl ${\alpha}$-Diketones (팔라듐 촉매를 이용한 디비닐케톤과 디비닐 ${\alpha}$-디케톤의 새로운 합성)

  • Jin Il Kim;Kwang Hyek Lee;Seung Jae Im
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.522-529
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    • 1989
  • Symmetrical divinyl ketones and divinyl ${\alpha}$-diketones were synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylic halides. Divinyl ${\alpha}$-diketones were obtained in the highest yield in the presence of 10 atm of carbon monoxide, using 2 mol% ligand added to palladium(II) acetate as catalyst and three equivalents of tributylamine as base in polar solvent at $100^{\circ}C$. Divinyl ketones were synthesized mainly under atmospheric pressure of carbon monoxide. The reaction was also proceeded to several other vinylic halides under the above reaction condition. Thus, divinyl ketones and divinyl ${\alpha}$-diketones were synthesized selectively as expected.

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Separation of Palladium(II) and Ruthenium(IV) from Hydrochloric Acid Solution by Solvent Extraction (염산용액에서 용매추출에 의한 팔라듐(II)과 루테늄(IV)의 분리)

  • Lee, Man-seung;Ahn, Jong-Gwan
    • Korean Journal of Metals and Materials
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    • v.47 no.6
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    • pp.349-355
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    • 2009
  • In the solvent extraction of Ru(IV) with Alamine336, it was found that Ru took part in the reaction as $RuCl_{6}_^{2-}$ in the HCl concentration range of 1 to 5 M. Interaction parameter between hydrogen ion and $RuCl_{6}_^{2-}$ was estimated by applying Bromley equation to the extraction data. From the mixed solutions of Pd(II) and Ru(IV), the distribution coefficients of Pd were found to be higher than those of Ru in the experimental ranges. Separation factor between Pd and Ru rapidly increased with the decrease of Alamine336 concentration. About 60% of the Ru from the mixed solutions was extracted by TBP at 8.3 M HCl, while Pd was not extracted in the HCl concentration range of 1.6 to 8.3 M.

Metal Complexes of Ambidentate Ligand (VIII). Ni (II) and Pd (II) Complexes of Isonitrosomethylacetoacetate Imines (Ambidentate 리간드의 금속착물 (제 8 보). Isonitrosomethylacetoacetate Imine 리간드의 니켈(II) 및 팔라듐(II) 착물)

  • Bon-Chang Goo;Gang-Yeol Choi;Man-Ho Lee;In-Whan Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.662-671
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    • 1993
  • New Ni(II) and Pd(II) complexes of isonitrosomethylacetoacetate imine derivatives, Ni(IMAA-NH)(IMAA-NH'), Ni(IMAA-NH)(IMAA-NR), $Pd(IMAA-NH)_2\;and Pd(IMAA-NR)_2(R=CH_3,\;C_2H_5,\;n-C_3H_7,\;n-C_4H_9,\;or\;CH_2C_6H_5)$, where H-IMAA-NH and H-IMAA-NR represent isonitrosomethylacetoacetate imine and N-alkylisonitrosomethylacetoacetate imine derivative, respectively, have been prepared and the structures of the complexes have been studied by elemental analyses, electronic, infrared, and $^1H-\;and\;^{13}C-NMR$ spectroscopies.

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Effect of Cu(II) and Al(III) on the Extraction and Separation of Pt(IV) and Pd(II) from Concentrated Hydrochloric Acid Solution with Alamine336 (진한 염산용액에서 구리(II)와 알루미늄(III)이 Alamine336에 의한 백금(IV)과 팔라듐(II)의 추출 및 분리에 미치는 영향)

  • Lee, Manseung;Ahn, Jonggwan;Sun, Panpan
    • Korean Journal of Metals and Materials
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    • v.48 no.2
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    • pp.148-153
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    • 2010
  • The effects of Cu(II) and Al(III) on the extraction and separation of Pt(IV) and Pd(II) have been investigated in a mixed chloride solution using Alamine336 as the extractant. In the HCl concentration range of 1 to 5 M, more than 99% of Pt and Pd could be extracted by Alamine336 from all of the mixed chloride solutions investigated in this study. Lower HCl concentration led to a higher separation factor between Pd and Pt when Alamine336 concentration was constant. Extraction percentage of Cu increased with the increase of HCl concentration, while that of Al was nearly constant at 33% in our experimental range. The optimum conditions to extract Pt and Pd from Cu or Al and the separation factor under these conditions were obtained.

Metal Complexes of Ambidentate Ligands (II). Cobalt (III) and Palladium (II) Complexes of Isonitrosobenzoylacetone (Ambidentate Ligand의 금속착물 (제2보). Isonitrosobenzoylacetone 의 코발트 (III) 및 팔라듐 (II) 착물)

  • Man Ho Lee;Dae Sup Oh;Soo Han Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.121-128
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    • 1980
  • Isonitrosobenzoylacetone is particularly interesting, as the isonitroso group has two potentially coordinating sites which can compete with the cabonyl groups in forming bonds with the metal ions. In this paper tris(isonitrosobenzoylacetonato)cobalt(III) and bis(isonitrosobenzoylacetonato)palladium(II) have been prepared, and their structures have been investigated. Spectroscopic studies lead to the conclusion that the both complexes do not contain an OH group in the chelated five-membered ring structure in which the ligand coordinates to metal through oxygen of the acetyl group and nitrogen of the isonitroso group. The coordination manner of this ligand is similar to that of isonitrosobenzoylacetone obtained by Patel and Haldar.

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The Preparation and its Chemical Properties of Palladium Complexes with a series of Cycloamine (Cycloamine 계의 팔라듐 착물의 합성과 그 화학적 성질)

  • Sang-Oh Oh;Duck-Young Chung
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.406-413
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    • 1985
  • We synthesized Pd(II) complexes containing sulfoxide and cycloamine series on the basis of the fact that many workers had the foresight to suggest anticancer activites using Pd(II) complexes with sulfur, nitrogen, or nucleic acid relatives as ligands particulary. The identification and characterization of these complexes are followed; content rates of atoms and molecular weights are confirmed by Elemental Analysis and Mass spectra, bonding of metal and ligands by UV-Vis. spectra and NMR spectra, and donor sites of ligands and configuration of complexes by IR spectra. These are yellow crystals, soluble in methanol and chloroform, and insoluble in H2O and the other common organic solvents.

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