• Title/Summary/Keyword: Palladium complexes

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Synthesis and Reactivity of the Pentacoordinate Organosilicon and -germanium Compounds Containing the C,P-Chelating ο-Carboranylphosphino Ligand [ο-C2B10H10PPh2-C,P](CabC,P

  • Lee, Tae-Gweon;Kim, Sang-Hoon;Kong, Myong-Seon;Kang, Sang-Ook;Ko, Jae-Jung
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.845-851
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    • 2002
  • The synthesis of the intramolecular donor - stabilized silyl and germyl complexes of the type ($Cab^c.p) MMe_2X$ (2a:M=Si, X=Cl;2b;M= Ge, X=Cl;2e;M=Si,X=H) was achieved by the reaction of $LiCab^c,p$ (1) with $Me_2SiClX$ and $Me_2GeCl_2$ respectively. The intramolecular M←P interacion in 2a-2c is provided by $^1H$, $13^C.$, $31^P$ and $29^Si$ NMR spectroscopy. The salt elimination reactions of dichlorotetramethyldisilane and -digermane with 1 afforded the $bis(\sigma-carboranylphosphino)disilane$ and disgermane [$(Cab^C.P)MMe_2]_2(4a;M$ = Si;4b: M=Ge). The oxidative addition reaction of 4a-4b with $pd_2(dba)_3CHCl_3afforded$ the bis(silyl)-and bis(germyl)-palladium complexes. The chloro-bridged dipalladium complexes were obtained by the reaction of 2a-2b with $pd_2(dba)_3CHCl_3$ The crystal structures of 5a and 7b were determined by X-ray structural studies.

Bulk Coordination Polymerization of Dicyclopentadiene (DCPD) by Pd Complexes Containing β-Ketoiminate or β-Diketiminate Ligands

  • Lee, Eung Jun;Kim, Ho Sup;Lee, Byoung Ki;Hwang, Woon Sung;Sung, Ik Kyoung;Lee, Ik Mo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4131-4136
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    • 2012
  • Several palladium complexes containing ${\beta}$-ketoiminate and ${\beta}$-diketiminate ligands successfully produced poly(DCPD) possibly via vinyl addition. It was found that catalysts with ${\beta}$-diketiminate ligands containing bulkier aryl substituents showed the highest activity in the presence of MAO as a cocatalyst. Purity of DCPD is quite essential for the higher activity and small amount of organic solvent such as $CH_2Cl_2$ and toluene is required to reduce the viscosity of the reactant mixture for the higher activity. $^1H$ NMR spectra of produced polymers with N,N-dimethylanilinium tetra(pentafluorophenyl)borate (N,N-DAPFAr"$_4$) show that 5,6-double bond of DCPD is removed with 2,3-double bond remaining. Produced poly(DCPD) with MAO cocatalyst is quite rigid and insoluble in common organic solvents but rather brittle.

Metal Complexes of Ambidentate Ligand (Ⅶ). Palladium (Ⅱ) Complexes of Isonitrosobenzoylacetone Diimine Derivatives (Ambidentate 리간드의 금속착물 (제 7 보). Isonitrosobenzoylacetone 디이민유도체를 리간드로 하는 팔라듐 (Ⅱ) 착물)

  • Choi, Gang-Yeol;Jun, Young-Sook;Baek, Jae-Bum;Lee, Man-Ho
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.667-672
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    • 1991
  • Two palladium(Ⅱ) complexes, N-(2-aminoethylisonitrosobenzoylacetone imino) chloropalladium(Ⅱ), PdCl(IBA)-en, and N-(3-aminopropylisonitrosobenzoylacetone imino) chloropalladium(Ⅱ), PdCl (IBA)-tn, have been prepared from the condensation of isonitrosobenzoylacetone (IBA) and diamine (ethylenediamine(en) or trimethylenediamine(tn)) in the presence of palladium(Ⅱ) ion. It is suggested that the Schiff base formed by condensation of an isonitrosobenzoylacetone and a diamine coordinates to the metal through three nitrogens of isonitroso (=N-O), C=N, and $NH_2$groups as a tridentate ligand. And also a chloride ion coordinates to the metal in addition to the Schiff base ligand to form a square-planar geometry.

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Submicrospheres as Both a Template and the Catalyst Source. Silica Submicro-reactor Dotted with Palladium Nanoparticles as Catalysts

  • Kim, Sung Min;Noh, Tae Hwan;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1127-1130
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    • 2013
  • Formation of the monodisperse submicrospheres consisting of ionic palladium(II) complexes, $[(Me_4en)Pd(L)]_2(X)_4$($Me_4en$ = N,N,N',N'-tetramethylethylenediamine; L = bis(4-(4-pyridylcarboxyl)phenyl)methane; $X^-=BF_4{^-}$ and $ClO_4{^-}$), has been carried out without any templates or additives. The submicrospheres were coated with silicates, and then calcined in air at $550^{\circ}C$ for 1 h, to efficiently form hollow-spherical $SiO_2$ submicro-reactors dotted with palladium(0) nanoparticles (PdNPs). That is, the submicrospheres act as both a template and a source of the palladium metal nanoparticles. The submicro-reactors containing nano-catalysts have been characterized by means of SEM, TEM, and XPS. Notably, the reactors were proved to be very effective for Suzuki-Miyaura cross-coupling and hydrogenation reactions.

Metal Complexes of Ambidentate Ligand (VI). Palladium(II) Complexes of Isonitrosoethylacetoacetate Imines (Ambidentate 리간드의 금속착물 (제 6 보). Isonitrosoethylacetoacetate Imine 리간드의 팔라듐 (II) 착물)

  • Jun Young-Sook;Lee Man-Ho;Kim In-Whan;Kim Soo-Han
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.368-373
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    • 1991
  • Palladium(II) complexes of the type Pd(IEAA-NR)$_2$ (R = H, CH$_3$, C$_2$H$_5$, n-C$_3$H$_7$, n-C$_4$H$_9$, or CH$_2$C$_6$H$_5$), where IEAA-NR represents N-alkyl derivative of isonitrosoethylacetoacetate (H-IEAA) imine, have been prepared. And the structure of the complexes have been studied by elemental analyses, electronic, infrared, $^1$H and $^{13}$C-NMR spectra. It is proposed that both of IEAA-NR ligands coordinate to metal through nitrogens of imine and isonitroso groups to form 5-membered chelate rings in the complexes.

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Synthesis and Characterization of Bis(silyl) Palladinum and -Platinum(II) Complexes (비스실릴팔라듐(II) 및 백금(II)착물의 합성 및 확인)

  • Cho, Jun-Churl;Kim, Yong-Joo
    • Journal of Integrative Natural Science
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    • v.2 no.3
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    • pp.190-193
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    • 2009
  • Bis(silyl)palladinum(II) and -platinum(II) complexes are key intermediates for the synthesis of organic silyllated compounds by the Pd or Pt-catalyzed reactions. Reactions of dialkylpalladinum and -platinum complexes with diphenylsilane gave the bis(silyl)palladinum and -platinum complexe in moderate to good yields. Isolated complexes were characterized by $^1H$, $^{13}C$ and $^{31}P$-NMR spectroscopy and elemental analyses. Some of the complexes were determined by X-ray crystallographic studies.

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Catalytic Activities of Pd(II), Pd(I) and Pd(O)-diphosphine Complexes for Styrene Oxidation

  • Jo, Yeong Je;Kim, Gyeong Chae;Jeong, Jong Hwa;Park, Yu Cheol;Do, Myeong Gi
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.211-214
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    • 1995
  • The catalytic activities of palladium(0,Ⅰ,Ⅱ)-diphosphine complexes were investigated in styrene oxidation using H2O2 as terminal oxidant. The rates showed a dependence on the chelate ring patterns of complexes (PdCl2L); 5-membered ring (L=dppe: 1,2-bis(diphenylphosphino)ethane) < 6-membered ring (L=dppp: 1,3-bis(diphenylphosphino)propane) < 4-membered ring (L= dppm: bis(diphenylphosphino)methane). This sequence correlates with the ligand field strength and interactions between metal and phosphine ligands. Pd(Ⅱ,Ⅰ)-diphosphine complexes which are capable of making 4-membered chelate ring showed an enhancement of catalytic activities for styrene oxidation. The catalytic activities of Pd(0,Ⅰ,Ⅱ)-diphosphine complexes are described in terms of electronic and steric factors.

DNA-Binding and Thermodynamic Parameters, Structure and Cytotoxicity of Newly Designed Platinum(II) and Palladium(II) Anti-Tumor Complexes

  • Mansouri-Torshizi, Hassan;Saeidifar, Maryam;Khosravi, Fatemeh;Divsalar, Adeleh;Saboury, Ali.Akbar;Ghasemi, Zahra Yekke
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.947-955
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    • 2011
  • The complexes [Pd(bpy)(Hex-dtc)]$NO_3$ and [Pt(bpy)(Hex-dtc)]$NO_3$ (bpy is 2,2'-bipyridine and Hex-dtc is hexyldithiocarbamato ligands) were synthesized and characterized by elemental analysis and spectroscopic studies. The cytotoxicity assay of the complexes has been performed on chronic myelogenous leukemia cell line, K562, at micromolar concentration. Both complexes showed cytotoxic activity far better than that of cisplatin under the same experimental conditions. The binding parameters of the complexes with calf thymus DNA (CT-DNA) was investigated using UV-visible and fluorescence techniques. They show the ability of cooperatively intercalating in CT-DNA. Gel filtration studies demonstrated that platinum complex could cleave the DNA. In the interaction studies between the Pd(II) and Pt(II) complexes with CT-DNA, several binding and thermodynamic parameters have been determined, which may provide deeper insights into the mechanism of action of these types of complexes with nucleic acids.