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1.
The reactions of AuIII, PtII and PdII complexes with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic (H2O, MeOH, EtOH) and aprotic (DMF, CH2Cl2) solvents. Compounds in which the pyridine ligand is N-coordinated, either in the original aldehydic form or in a new form derived from addition of one or two protic molecules, have been isolated, namely: [Au(2CHO-py · H2O)Cl3], [Au(2CHO-py · MeOH)Cl3], [Au(2CHO-py · 2EtOH)Cl3], cis-[Pt(2CHO-py)2Cl2], trans-[Pd(2CHO-py)2Cl2], trans-[Pt(dmso)(2CHO-py)Cl2], [Pt{C5H4N-(CH2SMe)}Cl(2CHO-py)](ClO4), [Pt(terpy)(2CHOpy)](ClO4)2, [Pt(terpy)(2CHO-py · H2O)](ClO4)2 (terpy = 2,2′:6′,2′′-terpyridine). 1H-n.m.r. experiments show that the addition of the protic molecule(s) to the PtII and PdII complexes is reversible. The effects of the nature of the metal ion and the ancillary ligands as well as of the total charge of the complexes on the relative stability of the addition products are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

2.
Summary Complexes of 2-mercapto-1-methylimidazole (TMZ) with PtII, PdII, RhIII and RuIII of the general formulae Pt(TMZ)2Cl2, Pd(TMZ)4Cl2. Rh(TMZ)Cl3 and Ru(TMZ)Cl3 have been obtained. The thermal stabilities of the compounds were estimated by derivatographic measurements and the electron-donating atom of the measurements and the electron-donating atom of the ligand was identified from the i.r. absorbtion spectra. Lattice constants for the PtII and PdII complexes were estimated from their x-ray powder diffraction patterns.  相似文献   

3.
The complex [Pt(5,5′-dmbipy)Cl4] (1) (5,5′-dmbipy is 5,5′-dimethyl-2,2′-bipyridine) was prepared from the reaction of H2PtCl6·6H2O with 5,5′-dimethyl-2,2′-bipyridine in methanol. The same method was employed to make [Pt(6-mbipy)Cl4] (2) (6-mbipy is 6-methyl-2,2′-bipyridine). Both complexes were characterized by elemental analysis, IR, UV–Vis, 1H NMR, 13C NMR and 195Pt NMR spectroscopy. Their solid state structures were determined by the X-ray diffraction method.  相似文献   

4.
The kinetics of some outer-sphere electron-transfer reactions with the participation of the complexes [Pt(NH3)nX6–n]2 (n=6–0, X=Cl, Br) and dipyridyl complexes of Os(II), Ru(II), Ir(III), and Cr(II) have been investigated by means of luminescence-quenching measurements and flash photolysis. Estimates of the values of the Pt(IV)/Pt(III) one-electron potential and the change in the free energy of activation of electron self-exchange processes of the type Pt(IV) Pt(III) have been obtained on the basis of an analysis of the dependence of the rate constant on the change in the free energy accompanying the electrontransfer process.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 4, pp. 455–462, July–August, 1990.  相似文献   

5.
Some news thiopyrimidine derivatives and complexes [4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidine (TANH), its 2-methylthio derivative (MTH), the ammonium salt ofTANH (sTANH) and six new complexes of formulas: Rh(MT)2Cl · 2H2O, Pd(MTH)2Cl2, Pt(MTH)2Cl4, Au(MTH)Cl3 Pd(TANH)2Cl2 and Au(TAN )Cl] have been synthesized and characterized by elemental analysis, IR and1H-NMR spectroscopy techniques. The thermal behaviour of all compounds has also been studied.
Rh(III), Pd(II), Pt(IV) und Au(III) Komplexe von 2-Thiopyrimidin Derivaten
Zusammenfassung Es wurden einige neue Thiopyrimidinderivate und deren Komplexe synthetisiert und mittels Elementaranalyse, IR und1H-NMR charakterisiert: 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidin (TANH), dessen 2-Methylthio-Derivat (MTH), das Ammoniumsalz vonTANH (sTANH) und sechs neue Komplexe der Formeln Rh(MT)2Cl · 2H2O, Pd(MTH)2Cl2, Pt(MTH)2Cl4, Au(MTH)Cl3, Pd(TANH)2Cl2 und Au(TAN )Cl. Das thermische Verhalten der Verbindungen wurde ebenfalls untersucht.
  相似文献   

6.
《Polyhedron》1999,18(26):3527-3531
The redox reaction between [Pt(NH3)4]2+ and [W(CN)8]3− in the presence of Cl anions in aqueous solution affords single crystals of [PtII(NH3)4]2[WIV(CN)8] and [PtIV(NH3)4Cl2]Cl2. Trapped cyano ligands of [W(CN)8]4− rectangular antiprisms of D2 point symmetry between parallel Pt(II) square planes show that the inner-sphere redox pathway is prohibited. The presence of Cl counterions enables the formation of [Pt(NH3)4Cl2]Cl2 as the product of the rare outer-sphere pathway of the oxidation of Pt(II) by [W(CN)8]3−.  相似文献   

7.
Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N3)6]2– and [Pt(N3)Cl5]2–, 195Pt and 15N NMR Spectra of [Pt(N3)nCl6–n]2– and [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 By ligand exchange of [PtCl6]2– with sodium azide mixed complexes of the series [Pt(N3)nCl6–n]2– and with 15N‐labelled sodium azide (Na15NN2) mixtures of the isotopomeres [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 and the pair [Pt(15NN2)Cl5]2–/[Pt(N215N)Cl5]2– are formed. X‐ray structure determinations on single crystals of (Ph4P)2[Pt(N3)6] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph4As)2[Pt(N3)Cl5] · HCON(CH3)2 ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with Nα–Nβ–Nγ‐angles = 173.5–174.6° are bonded with Pt–Nα–Nβ‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu4N)2[Pt(N3)Cl5] are observed at 318–345, the PtN stretching modes of (n‐Bu4N)2[Pt(N3)6] at 401–428 and of (n‐Bu4N)2[Pt(N3)Cl5] at 408–413 cm–1. The mixtures (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 and (n‐Bu4N)2[Pt(15NN2)Cl5]/(n‐Bu4N)2[Pt(N215N)Cl5] exhibit 15N‐isotopic shifts up to 20 cm–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are fd(PtCl) = 1.93, fd(PtNα) = 2.38 and fd(NαNβ, NβNγ) = 12.39 mdyn/Å. In the 195Pt NMR spectrum of [Pt(N3)nCl6–n]2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The 15N NMR spectrum of (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 exhibits by 15N–195Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal 15N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.  相似文献   

8.
Palladium(II) and platinum(II) complexes containing mixed ligands N-(2-pyridyl)acetamide (AH) or N-(2-pyrimidyl)acetamide (BH) and the diphosphines Ph2P(CH2) n PPh2, (n = 1, 2 or 3) have been prepared. The prepared complexes [Pd(A)2(diphos)] or [Pd(B)2(diphos)] have been used effectively to prepare bimetallic complexes of the type [(diphos)Pd(μ-L)2M′Cl2] where M′ = Co, Cu, Mn, Ni, Pd, Pt or SnCl2; L = A or B. The prepared complexes were characterized by elemental analysis magnetic susceptibility, i.r. and UV–Vis spectral data. 31P–{1H}-n.m.r. data have been applied to characterize the produced linkage isomers.  相似文献   

9.
The complexes [Pt(3′′‐clpbpy)Cl2] ( 1 ) [3′′‐clpbpy = 4‐(3′′‐chlorophenyl)‐6‐phenyl‐2, 2′‐bipyridine], [Pt(4′′‐clpbpy)Cl2] ( 2 ) [4′′‐clpbpy = 4‐(4′′‐chlorophenyl)‐6‐phenyl‐2, 2′‐bipyridine], [Pt(3′′‐brpbpy)Cl2] ( 3 ) [3′′‐brpbpy = 4‐(3′′‐bromophenyl)‐6‐phenyl‐2, 2′‐bipyridine], and [Pt(4′′‐brpbpy)Cl2] ( 4 ) [4′′‐brpbpy = 4‐(4′′‐bromophenyl)‐6‐phenyl‐2, 2′‐bipyridine] were synthesized and characterized. The binding of the complexes with herring sperm DNA (HS DNA) was investigated by absorption titration and viscosity measurements. It was found that the complexes have ability of interaction with DNA by covalent mode. The intrinsic binding constant Kb of the complexes with HS DNA is 8.76 × 104 ( 1 ), 9.89 ×104 ( 2 ), 1.52 × 105 ( 3 ), and 2.31 × 105 ( 4 ) M–1. The slight depression in relative specific viscosity was observed, which also attributes to covalent binding of complexes with DNA bases. Gel electrophoresis assay demonstrated the ability of the complexes to unwind negatively supercoiled pUC19 plasmid by 14° ( 1 ), 13° ( 2 ), 13° ( 3 ), and 11° ( 4 ). The in vitro cytotoxic property of the synthesized metal complexes was also carried out against brine shrimp bioassay.  相似文献   

10.
Sodium thiosulfate has been utilized as a rescuing agent for relief of the toxic effects of cisplatin and carboplatin. In this work, we characterized the kinetics of reactions of the trans-dichloro-platinum(IV) complexes cis-[Pt(NH3)2Cl4], ormaplatin [Pt(dach)Cl4] and trans-[PtCl2(CN)4]2? (anticancer prodrugs and a model compound) with thiosulfate at biologically important pH. An overall second-order rate law was established for the reduction of trans-[PtCl2(CN)4]2? by thiosulfate, and varying the pH from 4.45 to 7.90 had virtually no influence on the reaction rate. In the reactions of thiosulfate with cis-[Pt(NH3)2Cl4] and with [Pt(dach)Cl4], the kinetic traces displayed a fast reduction step followed by a slow substitution involving the intermediate Pt(II) complexes. The reduction step also followed second-order kinetics. Reductions of cis-[Pt(NH3)2Cl4] and [Pt(dach)Cl4] by thiosulfate proceeded with similar rates, presumably due to their similar configurations, whereas the reduction of trans-[PtCl2(CN)4]2? was about 1,000 times faster. A common reduction mechanism is suggested, and the transition state for the rate-determining step has been delineated. The activation parameters are consistent with transfer of Cl+ from the platinum(IV) center to the attacking thiosulfate in the rate-determining step.  相似文献   

11.
Naphthaldimines containing N2O2 donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H2L1)PtCl2]·3H2O (1) and [(H2L3)2Pt2Cl4]·5H2O (3), or monobasic [(HL2)2Pt2Cl2]·2H2O (2) and [(HL4)2Pt]·2H2O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L1)Pt2Cl4(OH)2]·2H2O (5), [(L2)Pt3Cl10]·3H2O (6), [(L3)Pt2Cl4(OH)2]·C2H5OH (7) and [(L4)Pt2Cl6]·H2O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.  相似文献   

12.
Stereoisomeric Pt(IV) complexes with threonine (ThrH = HOCH(CH3)CH(NH2)COOH, ??-amino-??-hydroxybutyric acid) were obtained. In the complexes trans-[Pt(S-ThrH)2Cl4] and trans-[Pt(R-ThrH)(S-ThrH)Cl4], the ThrH molecules act as monodentate ligands coordinated through the NH2 group. In the complexes cis- and trans-[Pt(S-Thr)2Cl2] and trans-[Pt(R-Thr)(S-Thr)Cl2], the deprotonated ligands are coordinated in a bidentate fashion through the NH2 and COO?-groups (R,S is the absolute configuration of the asymmetric carbon atom). All the complexes were identified using elemental analysis, IR spectroscopy, and 195Pt, 13C, and 1H NMR spectroscopy. The complexes trans-[Pt(S-ThrH)2Cl4] · 3H2O and cis-[Pt(S-Thr)2Cl2] · 2H2O were additionally characterized by X-ray diffraction.  相似文献   

13.
1H, 13C and 15N NMR studies of gold(III), palladium(II) and platinum(II) chloride complexes with picolines, [Au(PIC)Cl3], trans‐[Pd(PIC)2Cl2], trans/cis‐[Pt(PIC)2Cl2] and [Pt(PIC)4]Cl2, were performed. After complexation, the 1H and 13C signals were shifted to higher frequency, whereas the 15N ones to lower (by ca 80–110 ppm), with respect to the free ligands. The 15N shielding phenomenon was enhanced in the series [Au(PIC)Cl3] < trans‐[Pd(PIC)2Cl2] < cis‐[Pt(PIC)2Cl2] < trans‐[Pt(PIC)2Cl2]; it increased following the Pd(II) → Pt(II) replacement, but decreased upon the transcis‐transition. Experimental 1H, 13C and 15N NMR chemical shifts were compared to those quantum‐chemically calculated by B3LYP/LanL2DZ + 6‐31G**//B3LYP/LanL2DZ + 6‐31G*. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

14.
A new series of platinum(II) complexes based on thione ligands with general formula [Pt(thione)4]X2 (X??=?Cl?, NO3?) has been synthesized and characterized using CHNS elemental analysis, infrared, 1H and 13C solution-state NMR as well as 13C and 15N solid-state NMR spectroscopy, and X-ray crystallography. The spectroscopic methods confirm the coordination of Pt(II) with thiocarbonyl groups via sulfur of the thione ligands. The X-ray structures showed a distorted square planar geometry for 1, [Pt(MeImt)4]Cl2 (MeImt = N-Methylimidazolidine-2-thione) while the hydrogen bonding interactions in 7, [Pt(iPrImt)4](NO3)2·0.6(H2O) induce a bent see-saw distortion relative to the ideal square planar geometry. The in vitro cytotoxicity studies showed that 2, [Pt(EtImt)4]Cl2 is generally the most effective, a two-fold better cytotoxic agent than cisplatin and carboplatin against MCF7 (human breast cancer).  相似文献   

15.
Water adsorption on Pt(111) surfaces treated with oxygen or hydrogen chloride at 20 K has been studied by Fourier transform infrared spectroscopy and scanning tunneling microscopy. Water molecules chemisorb predominantly on the sites of the electronegative additives (O or Cl-), forming hydrogen bonds of O-HO or O-HCl-. On a Pt(111)-2×2-O surface, water adsorption produces species (O(D2O)), monomeric water (D2O), (O(D2O)2) and ring tetramer-like cluster (O(D2O)3) on a Pt(111) surface. On a Pt(111)-3×3-Cl- (θ=0.44) surface, water adsorption gives rise to a Pt(111)-(4×2)-(H3O++Cl-) co-adsorption structure to form a hydrogen-bonding network between Cl- and H3O+ ions.  相似文献   

16.
The compounds [(PPh3)2,RPtHgR′] (R = CH3, R′= 2,5-C6H3Cl2, 2,3,4- and 2,4,6-C6H2Cl3, 2,3,4,5-, 2,3,4,6- and 2,3,5,6-C6HCl4, C6Cl5; R = Et, R′ = 2,5-C6H3Cl2, 2,4,6-C6H2Cl3; R = 2-C6H4Cl, R′=2-C6H4(CH3)) have been prepared by the reactions of RHgR′ with Pt(PPh3)3, in order to study their possible use as intermediates in the preparation of diorganoplatinum complexes with different organic ligands. The dependence of J(31P-195Pt) on slight differences in the electronic character of the ligand R′ in the series of compounds [(PPh3)2(CH3)Pt-HgR′] has been studied.  相似文献   

17.
Poly(triazine imide) was synthesized with incorporation of Li+ and Cl? ions (PTI/Li+Cl?) to form a carbon nitride derivative. The synthesis of this material by the temperature‐induced condensation of dicyandiamide was examined both in a eutectic mixture of LiCl–KCl and without KCl. On the basis of X‐ray diffraction measurements of the synthesized materials, we suggest that a stoichiometric amount of LiCl is necessary to obtain the PTI/Li+Cl? phase without requiring the presence of KCl at 873 K. PTI/Li+Cl? with modification by either Pt or CoOx as cocatalyst photocatalytically produced H2 or O2, respectively, from water. The production of H2 or O2 from water indicates that the valence and conduction bands of PTI/Li+Cl? were properly located to achieve overall water splitting. The treatment of PTI/Li+Cl? with [Pt(NH3)4]2+ cations enabled the deposition of Pt through ion exchange, demonstrating photocatalytic activity for H2 evolution, while treatment with [PtCl6]2? anions resulted in no Pt deposition. This was most likely because of the preferential exchange between Li+ ions and [Pt(NH3)4]2+ cations.  相似文献   

18.
《Analytical letters》2012,45(12):2182-2193
K[Pt(NH3)Cl3], a valuable precursor for the preparation of platinum complexes with cytostatic activity, e.g. satraplatin, picoplatin, LA-12 and cycloplatam, is currently prepared from cis-[Pt(NH3)2Cl2] or K2[PtCl4] and these are the usual impurities in the final product. A simple, selective and sensitive HPLC-UV analytical method for the determination of the purity of K[Pt(NH3)Cl3] and the quantification of the impurities has been developed and validated. The platinum complexes present in the final product were separated on a strong base ion exchange column by the gradient elution with detection at 213 nm. Intra-assay precisions for the platinum complexes respective to their ions ([PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2]) were between 0.1 and 2.0% (relative standard deviation); intermediate precisions were between 1.4 and 2.0% and accuracies were between 98.6 and 101.4%. Limits of detection of [PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2] were 6 µg · ml?1, 13 mg · ml?1 and 5 µg · ml?1 respectively, limits of quantification of [PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2] were 51 µg · ml?1, 55 mg · ml?1 and 20 µg · ml?1 respectively.  相似文献   

19.
Nickel(II) chalcogenolate complexes [Ni(L-L)2(dppe) Cl2] (1, 2) have been prepared in high yields by reacting 1,2-diarylchalcogenolato-o-xylene, o-C6H4(CH2EAr)2 (E = Se or Te; Ar = Ph, C6H4OMe-4 and C6H4OEt-4), generated in situ, with Ni(dppe)Cl2 [dppe = 1,2-bis(diphenylphosphino)ethane] in benzene. The structures were established by elemental analyses, molar conductance, i.r. and Raman, electronic 1H- and 31P-n.m.r. and mass spectral data. The analytical and spectroscopic data are consistent with an octahedral geometry around nickel in (1) and (2). The 31P-n.m.r. spectra indicate their cis configuration in solution. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

20.
Summary Platinum(II) and palladium(II) chloride complexes with purine, pyrimidine (pyrimid),N-ethylimidazole(N-EtIm) andN-propylimidazole(N-PropIm) ligands have been prepared and characterized by analysis and spectroscopic methods. The compounds have general formula M(L1)(L2)Cl2 where M=PtII, PdII; L1=purine or pyrimid, L2=N-EtIm orN-PropIm, except the complexes Pt(purine)(pyrimid)Cl2 and [Pd(purine)(pyrimid)2Cl]Cl and [Pt(purine)2 (N-propIm)Cl]Cl·2H2O.  相似文献   

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