• Title/Summary/Keyword: platinum complex

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Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

Platinum Transporters and Drug Resistance

  • Choi, Min-Koo;Kim, Dae-Duk
    • Archives of Pharmacal Research
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    • v.29 no.12
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    • pp.1067-1073
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    • 2006
  • Cisplatin, a platinum coordinated complex, is a widely used antineoplastic agent for the treatment of metastatic tumors of the testis, metastatic ovarian tumors, lung cancer, advanced bladder cancer and many other solid tumors. The cytotoxic action of the drug is often thought to be associated with its ability to bind DNA to form cisplatin-DNA adducts. The development of resistance to cisplatin during treatment is common and constitutes a major obstacle to the cure of sensitive tumors. Although to understand the clinically relevant mechanisms of resistance, many studies have been aimed at clarifying the biochemical/molecular alterations of cisplatin-resistance cells, these studies did not conclusively identify the basis of cellular resistance to cisplatin. In this review, cisplatin resistance was discussed in terms of the relevant transporters, such as copper transporters (CTRs), organic cation transporters (OCTs) and multi-drug resistance related transporters (MDRs). These transporters seem to be contributed to cisplatin resistance through the reduction of drug accumulation in the cell. Better understanding the mechanism of cisplatin resistance associated with transporters will provide the useful informations for overcoming the cisplatin resistance.

Stereoselective Reactions of 2,3-Diaminobutane with Platinum(Ⅱ). Complexes of Optically Active 6,6$^\prime$-Dimethyl-2,2$^\prime$-diaminobiphenyl

  • Jun, Moo-Jin;Choi, Sung-Rack
    • Bulletin of the Korean Chemical Society
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    • v.6 no.2
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    • pp.119-120
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    • 1985
  • Stereospecific coordination of racemic 2,3-diaminobutane has been observed in the reaction with platinum(Ⅱ) complexes of optically active 6,6'-dimethyl-2,2'-diaminobiphenyl. The reaction between [Pt (R-dmdabp) Cl$_{2}$] (R-dmdabp is R-6,6'-dimethyl-2,2'-diaminobiphenyl) and unresolved bn (bn is 2,3-diaminobutane) has yielded [Pt(R-dmdabp)-(R-bn)] Cl$_{2}$ only, while the reaction of [Pt(S-dmdabp)Cl$_{2}$] with unresolvd bn has yielded [Pt(S-dmdabp) (S-bn)]Cl$_{2}$ only. On the other hand, the standard [Pt(R-dmdabp) (R-bn)] Cl$_{2}$ complex has been independently prepared from the reaction of [Pt(R-dmdabp)Cl$_{2}$] with R-bn, and the standard [Pt(S-dmdabp) (S-bn)] Cl$_{2}$ from the reaction of [Pt(S-dmdabp)Cl$_{2}$] with S-bn. The stereospecific behavior of the racemic 2,3-diamino-butane is thus confirmed from the comparison of these Pt(Ⅱ) complexes prepared using racemic bn with the standard Pt(Ⅱ) complexes prepared using R-bn or S-bn.

Poly(3,4-ethylenedioxythiophene) Electrodes Doped with Anionic Metalloporphyrins

  • 송의환;여인형;백운기
    • Bulletin of the Korean Chemical Society
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    • v.20 no.11
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    • pp.1303-1308
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    • 1999
  • Conducting poly(3,4-ethylenedioxythiophene) (PEDT) films with metalloporphyrins incorporated as the counter ions were prepared by electropolymerization of the monomer in the presence of metal-tetra(sulfonatophenyl) porphyrin anions. Cathodic reduction of oxygen on the resulting conducting polymer films was studied. The overpotential for O2 reduction on electrodes with cobalt-porphyrin complex was significantly smaller in acidic solutions than on gold. In basic solutions, the overpotential at low current densities was close to those on platinum and gold. Polymer electrode with Co-complex yielded higher limiting currents than with Fe-complex, although the Co-complex polymer electrode was a poorer electrocatalyst for O2 reduction in the activation range of potential than the Fe counterpart. From the rotating ring-disk electrode experiments, oxygen reduction was shown to proceed through either a 4-electron pathway or a 2-electron pathway. In contrast to the polypyr-role-based electrodes, the PEDT-based metalloporphyrin electrodes were stable with wider potential windows, including the oxygen reduction potential. Their electrocatalytic properties were maintained at temperatures up to 80℃ in KOH solutions.

Oxidative Addition Reaction of Mono(aryl)cyanoplatinum(Ⅱ) Complex with Two Amino Ligands with the Dihalogens

  • Ko Jaejung;Kim Moonsik;Kim Seho;Shin Yookil
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.135-139
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    • 1992
  • The mono(aryl)cyanoplatinum(II) complex $[Pt(CN)(C_6H_3{CH_2NMe_2}_2-26)]$, reacts with the dihalogens to yield the mono(aryl)cyanoplatinum complexes $[PtX_2(CN)(C_6H_3{CH_2NMe_2}_2-26)]$, (X = Cl, Br, I). The structural configuration of the two halogen atoms for a square planar platinum complex was studied by 1H-NMR spectroscopy and led to a mixture of trans and cis orientation. The trans orientation was found to be more stable in energy (1.33 kcal/mol) than the cis orientation by means of Extended H ckel calculations. On the base of a combination of the analysis of $^1H-NMR$, $^{13}C-NMR spectra and computational calculations it is assumed that the intermediate consists of an initial attack in the linear transition state, leading to the $S_{N}2$ type mechanism.

Synthesis and Properties of Novel Pt(II)-containing Polyphosphazenes

  • 백형기;정옥상;성용길;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.16 no.11
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    • pp.1074-1079
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    • 1995
  • Poly(dichlorophosphazene) having low molecular weight (M&bar;w∼104) was synthesized by the thermal reaction of hexachlorocyclotriphosphazene in the presence of excess AlCl3 (>2%) as catalyst. Using the poly(dichlorophosphazene), poly[bis(ethylglycino)phosphazene], poly[bis(glycinemethylamido)phosphazene], and poly[(glycinemethylamido)(methylamino)phosphazene] were prepared. Diammineplatinum(Ⅱ) complex cation was introduced into these derivatized phosphazene polymers, and the resultant polymers containing the platinum(Ⅱ) moiety were charaterized by means of elemental analysis, IR and NMR spectroscopies, and then subjected to in vitro and in vivo assays of antitumor activity.

Optimization of Platinum amount in Pt/C for PEMFC (PEMFC 용 Pt 담이 촉매의 Pt 담지비에 따른 성능변화)

  • Cho Y.H.;Cho Y.H.;Park H.S.;Sung Y.E.
    • Proceedings of the Korean Society of Precision Engineering Conference
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    • 2006.05a
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    • pp.547-548
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    • 2006
  • This study focuses on a determination of amount of Pt in the Pt/C for catalysts of polymer electrolyte membrane fuel cells (PEMFC). PEMFC offer low weight and high power density and being considered fur automotive and stationary power applications. The PEMFC behavior is quite complex is influenced by several factors, including catalysts and structure of electrode and membrane type. Catalyst of electrode is important factor for PEMFC. One of the obstacles preventing polymer electrolyte membrane fuel cells from commercialization is the high cost of noble metals to be used as catalyst, such as platinum. To effectively use these metals, they have to be will dispersed to small particles on conductive carbon supports. The optimal amount of Pt in Pt/C was investigated by using polarization curves in single cell with $H_2/O_2$ operation.

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Preparation and Structure of [1,2-Bis(diphenylphosphino)ethane](nitrato)(trifluoromethylsulfonato)platinum(II): [Pt(dppe)($NO_3$)($CF_3SO_3$)] ([1,2-Bis(diphenylphosphino)ethane](nitrato)(trifluoromethylsulfonato)platinum(II)의 합성 및 구조: [Pt(dppe)($NO_3$)($CF_3SO_3$)])

  • Huh, Hyun-Sue;Lee, Soon-W.
    • Korean Journal of Crystallography
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    • v.19 no.1
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    • pp.21-24
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    • 2008
  • The title complex [Pt(dppe)($NO_3$)($CF_3SO_3$)] (dppe=1,2-bis(diphenylphosphino)ethane, $Ph_2PCH_2CH_2PH_2$) was prepared by sequentially treating [Pt(dppe)$Cl_2$] with 1 equiv of $AgNO_3$ and 1 equiv AgOTf (OTf=$CF_3SO_3$). The Pt metal is coordinated by two phosphorous atoms of the dppe ligand, one oxygen atom of the nitrato ($NO^-_3$) ligand, and one oxygen atom of the triflato(trifluoromethylsulfonato, $OTf^-$) ligand. The coordination sphere of Pt metal can be described as a distorted square plane.

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.

Synthesis and Characterization of Phosphorescent Platinum and Iridium Complexes of 6-Chloro-3-phenylpyridazine

  • Lee, Sang-Jin;Seok, Kang;Lee, Jae-Sung;Lee, Seung-Hee;Hwang, Kwang-Jin;Kim, Young-Kwan;Kim, Young-Sik
    • Journal of Photoscience
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    • v.10 no.2
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    • pp.185-187
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    • 2003
  • The preparation and the photophysics of organometallic Pt(II) and Ir(III) complexes with 6-ch1oro-3-phenylpyridazine (H6Clppdz) are reported. $K_2$PtCl$_4$ and IrCl$_3$ㆍn$H_{2}O$ cleanly cyclometalate with H6Clppdz, forming the corresponding chloro-bridged dimers, (6Clppdz)Pt($\mu$-Cl)$_2$Pt(6Clppdz) and (6Clppdz)$_2$Ir($\mu$-Cl)$_2$Ir(6Clppdz)$_2$ in good yield. These chloro-bridged dimers are cleaved with acetylacetone (Hacac) to give the corresponding monomer, (6Clppdz)Pt(acac) and (6Clppdz)$_2$ Ir(acac), respectively. Both complexes show bright orange luminescence at room temperature and the emission wavelengths are different depending on the metal and the structure of complexes. (6Clppdz)Pt(acac) shows two sharp emission bands in shorter wavelength ($\lambda$$_{em}$=541 and 580 nm), while (6Clppdz)$_2$ Ir(acac) shows a broad emission band in longer wavelength ($\lambda$$_{em}$=615 nm). Strong spinorbit coupling due to the heavy metal atom allows for the formally forbidden mixing of the $^1$MLCT with the $^3$MLCT and $^3$$\pi$-$\pi$$^{*}$ states.

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