Platinum Chelates Research Articles

Formation and structure of reaction products of cis‐PtCl2(NH3)2 with d(ApG) and/or d(GpA) in di‐, tri‐ and penta‐nucleotides

The reaction products of cis-PtCl2(NH)3)2 with several deoxyribonucleotides containing d(ApG) and/or d(GpA) have been studied. The various reaction products were separated by high-performance liquid chromatography and characterized by means of absorbance at 254 nm in combination with atomic absorption spectroscopy and 300-MHz 1H-NMR (pH dependence of the non-exchangeable base-protons, T1 relaxation time determinations). For the larger fragments the results from these techniques were confirmed by enzymatic degradation studies of the platinated fragments. The smallest of the investigated nucleotides, d(ApG) and d(GpA), both formed a variety of different platinum chelates. In the reaction with d(ApG) 15% cis-Pt(NH3)2-[d(ApG)N1(1),N7(2)] and 78% cis-Pt(NH3)2[d(ApG)N7(1),N7(2)] were found, 4% of the reacted material consisted of a 1 mol Pt/2 mol dinucleotide product, and 3% of an unidentified 1:1 product. From the main product two rotamers were found to occur: at room temperature, 81% anti,anti and 19% anti,syn product is present. With d(GpA) about equal amounts of N1,N7 and N7,N7 products were found; for both products the anti,anti and anti,syn conformations were found, respectively. Upon reaction of cis-PtCl2(NH3)2 with d(pApG) and d(pGpA) only the N7,N7 products were found; at room temperature and pH greater than 1.5 these products were present in anti,anti conformation. However, for the d(pApG)-platinum chelate at -20 degrees C a small amount (less than 5%) of a second product could be observed in NMR. For the d(pGpA)-platinum chelate a second N7,N7-coordinated product was observed when the pH of the NMR sample was lowered to 1.1 (at this pH the free 5'-phosphate group is protonated). With the larger fragments d(ApGpA), d(pApGpA) and d(TpApGpApT) the intra-molecular competition between the formation of the d(ApG) or the d(GpA) chelates could be studied. Using these nucleotides no N1-coordinated products or rotamers were observed. In the case of d(ApGpA) and d(TpApGpApT) the d(GpA) chelate (67% and 75% respectively) was favoured over the d(ApG) chelate, while with d(pApGpA) about equal amounts of both chelates were formed.

Monothio-β-Diketonate Transition Metal Complexes Having A Trifluoromethyl Substituent

Abstract The synthesis of twenty three complexes of cobalt(III), nickel(II), palladium(II), platinum(II), copper(II) and zinc(II) having three novel monothio-β-diketones, RC(SH)[dbnd]CHCOCF3, (R [dbnd] 3′-fluorophenyl, 4′-propylphenyl and 2′,4′,5′-triethoxyphenyl) and the known ligand with R as 2′-furyl is reported. Their dipole moments were determined in benzene solution at 25°C by static-polarization measurement. The dipole moment data of the four-coordinate nickel, palladium and platinum chelates clearly indicates a cis-square planar configuration. 1H and 19F NMR spectral data confirm the facial configuration of the six-coordinate cobalt(III) complexes. The four-coordinate zinc complexes have a tetrahedral structure and the copper complexes are believed to have a distorted cis-square planar structure.

Applications of fused-silica wall-coated open-tubular columns : II. Non-fluorinated Schiff base chelates

The gas chromatography on fused-silica capillary columns are reported for seventeen transition metal complexes on non-fluorinated Schiff base ligands, including aminothione ligands. Data presented include chromatograms showing various group separations, column activity effects, detection limits, specific retention volumes, rate constants for the chelate decompositions and enthalpies for the solution processes in the bonded stationary phases. The fused-silica columns were found to be generally superior to packed columns, particularly with regard to peak symmetry and resolution. However, activity effects were still evident, with distinct contributions from reversible adsorption, irreversible adsorption and catalysis being observed. The reactive nature of some of the chelates, notably the aminothione chelates and palladium and platinum chelates, seems to preclude their utilization for analytical purposes.

Cytidylyl (3'-5')guanosine dinucleotides give two platinum chelates with cis-diamminedichloroplatinum that are cytidine syn-anti conformational isomers

CpG et d(pCpG) reagissent avec cis-[PtCl 2 (NH 3 ) 2 ] ou cis-[Pt(NH 3 ) 2 (H 2 O) 2 ](NO 3 ) 2 dans l'eau a pH 5,5 en donnant un compose d'addition CN3-GN7 du reste cis-Pt(NH 3 ) 2 2+ . Reaction en 2 etapes

ChemInform Abstract: CONFORMATIONS OF (1,3‐DIAMINE)PLATINUM(II) CHELATES AS STUDIED BY CARBON‐13 AND PROTON NMR SPECTROSCOPY

Chemischer InformationsdienstVolume 12, Issue 39 Physical Organic Chemistry ChemInform Abstract: CONFORMATIONS OF (1,3-DIAMINE)PLATINUM(II) CHELATES AS STUDIED BY CARBON-13 AND PROTON NMR SPECTROSCOPY J. E. SARNESKI, J. E. SARNESKISearch for more papers by this authorL. E. ERICKSON, L. E. ERICKSONSearch for more papers by this authorC. N. REILLEY, C. N. REILLEYSearch for more papers by this author J. E. SARNESKI, J. E. SARNESKISearch for more papers by this authorL. E. ERICKSON, L. E. ERICKSONSearch for more papers by this authorC. N. REILLEY, C. N. REILLEYSearch for more papers by this author First published: September 29, 1981 https://doi.org/10.1002/chin.198139070AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume12, Issue39September 29, 1981 RelatedInformation

Platinum(II) and palladium(II) complexes of some chelating poly-fluoroalkyldithioethanes

Platinum(II) halide complexes of the chelating ligands CF3SCH2CH2SCF3, CF3SCHMeCH2SCF3, and C6F5SCH2CH2SC6F5 and platinum(II) and palladium(II) complexes of CF3SCH2CH2SCH3, CH3SCF2, CH2SCH3, CH3SCH(CF3)CH2SCH3, CH3SCH(CF3)CH(CF3)SCH3, and C6F5SCH2CH2SCH3 are described. N.m.r. spectroscopy shows the presence of isomers for each complex with rapid ring-conformational changes but slow inversion at sulphur on an n.m.r. time scale. Detailed 19F n.m.r. studies allow specific isomers to be identified in many cases. Low-temperature 19F n.m.r. studies on [Ptl2{CH3SCH(CF3)CH(CF3)SCH3}] show a barrier to ring-conformational changes, the first such barrier observed for five-membered chelate rings.

Kinetic studies of ring closures in platinum(II) chelates. Rate constants and activation parameters for chelation of platinum(II) by bis(2-aminoethyl) sulfide in aqueous solution

Kinetic studies of ring closures in platinum(II) chelates. Rate constants and activation parameters for chelation of platinum(II) by bis(2-aminoethyl) sulfide in aqueous solution

Gas chromatography of transition metal derivatives of the sulphur analogues of 4,4′-(ethane-1,2-diyldiimino)bis-(pent-3-en-2-one)

The thermoanalytical and gas chromatographic behaviour of the copper(II), nickel(II), zinc(II), cadmium(II), palladium(II) and platinum(II) chelates of 4,4′- (ethane-1,2-diyldiimino)bis(pent-3-ene-2-thione) and the copper(II) and nickel(II) chelates of 4-[(3-oxo-1-methylbut-1-enyl)aminoethylamino]pent-3-ene-2-thione are reported here for the first time. With exception of the cadmium chelate, the derivatives elute as sharp, symmetrical peaks at microgram levels without extensive decomposition. Detection limits with flame ionization detection were in the range 0.2–1.5 ng of metal. A nearly complete separation of five chelates of the first ligand is demonstrated. The use of this reagent for the simultaneous determination of copper, nickel and zinc has been examined.

Thio derivatives of β-diketones and their metal chelates. XIX. Metal chelates of two new fluorinated Monothio-β-diketones and their mass spectra

The nickel(II), palladium(II), platinum(II), copper(II), zinc(II) and rhodium(III) chelates of the new fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Pri, Bui) and the iron(III), ruthenium(III) and cobalt(III) chelates of PriC(SH)=CHCOCF3 have been prepared. The mass spectra of all but the two copper chelates have been obtained. The novel features of the spectra are the occurrence of the ions M-(R-H), M-R, and M-LH and the loss of H2S from the ions M-LH and M-L.

Dipole-moment measurements of metal chelates. Part II. Dipole moments of nickel(II), palladium(II), platinum(II), and cobalt(III) complexes of six fluorinated mercapto-β-diketones

Dipole moments have been determined by static polarization measurements for the nickel(II), palladium(II), platinum(II), and cobalt(III) chelates of the fluorinated mercapto-β-diketones RC(SH):CHCOCF3(R =m-MeC6H4, m-ClC6H4, m-BrC6H4, p-FC6H4, pClC6H4, and m,p-Cl2C6H3). The moments indicate cis-square-planar configurations for the nickel, palladium, and platinum complexes and suggest a facial-octahedral configuration for the cobalt complexes. The variation of the dipole moments with R is considered to be dependent on: (a) the magnitude and vector directions of the Ph–X bond moments; (b) the inductive effect of the meta- and para-substituent on the phenyl ring; and (c) the mesomeric effect of the substituent X.

Chelating monoolefinaniline complexes of platinum(II)

Bidentate ligands containing an olefin and an aniline, or N-substituted aniline, nitrogen donor have been synthesized, and platinum(II) chelates prepared for them.

Thio derivatives of β-diketones and their metal chelates. XIV. Mass spectra of palladium and platinum chelates of some fluorinated Monothio-β-diketones

The mass spectra of the palladium(11) and platinum(11) chelates of the fluorinated monothio-β- diketones, RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, p-BrC6H4, p-NO2C6H4, 2-thienyl), and of the palladium chelate of CH3C(SH)=CHCOCF3 have been obtained. The platinum chelates give rise to more metal-containing peaks than the palladium chelates. Mechanisms are proposed for the reactions involving the metal-containing fragments. A comparison of the mass spectra of the zinc, nickel, palladium and platinum chelates of these fluorinated monothio-β-diketones reveals that the fragmentation pattern is determined by the metal.

Thio derivatives of 1,3-diketones and their metal complexes. Nickel(II), palladium(II), and platinum(II) chelates of ethoxythioacetothioacetate

Thio derivatives of 1,3-diketones and their metal complexes. Nickel(II), palladium(II), and platinum(II) chelates of ethoxythioacetothioacetate

Stepwise formation of palladium(II), platinum(IV), gold(III) and bismuth(III) chelates with aspartic and glutamic acids

Stepwise formation of palladium(II), platinum(IV), gold(III) and bismuth(III) chelates with aspartic and glutamic acids

Thio derivatives of β-diketones and their metal chelates. XII. Dipole moments of the nickel(II), palladium(II), and platinum(II) chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one

Thio derivatives of β-diketones and their metal chelates. XII. Dipole moments of the nickel(II), palladium(II), and platinum(II) chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one