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1.
Michael W. Jones Robert M. Adlington Jack E. Baldwin Delphine D. Le Pevelen Nicolas Smiljanic 《Inorganica chimica acta》2010,363(6):1097-3600
Three new palladium(II) complexes incorporating the bispyrazolylmethane core have been synthesised and fully characterised in the solution and solid state. Single crystal X-ray studies revealed almost complete blocking of the upper face of the palladium ion by the substituents at the 3- and 5-positions of the pyrazole rings. Preliminary screening of the complexes for palladium(II) mediated catalysis revealed good catalytic activity for the Heck coupling reaction. 相似文献
2.
Two new 3,5-dimethylpyrazolic derived ligands that are N1-substituted by diamine chains, 1-[2-(diethylamino)ethyl]-3,5-dimethylpyrazole (L1) and 1-[2-(dioctylamino)ethyl]-3,5-dimethylpyrazole (L2) were synthesised. Reaction of the ligands, L1 and L2, with [MCl2(CH3CN)2] yielded [MCl2(L)] (M = Pd(II), Pt(II)) complexes. These complexes were characterised by elemental analyses, conductivity measurements, IR, 1H, 13C{1H} and 195Pt{1H} NMR spectroscopies. The crystal structure of [PdCl2(L1)] was determined by single-crystal X-ray diffraction methods. The structure consists of mononuclear units. The Pd(II) atom is coordinated by a pyrazolic nitrogen, an amine nitrogen and two chlorine atoms in a cis disposition. In this structure, C-H?Cl, C-H?H-C and C-H?C-H intermolecular interactions have been identified. 相似文献
3.
In vitro antitumour activity of the [Pt(ox)(Ln)2] (1-7) and [Pd(ox)(Ln)2] (8-14) oxalato (ox) complexes involving N6-benzyl-9-isopropyladenine-based N-donor carrier ligands (Ln) against ovarian carcinoma (A2780), cisplatin resistant ovarian carcinoma (A2780cis), malignant melanoma (G-361), lung carcinoma (A549), cervix epitheloid carcinoma (HeLa), breast adenocarcinoma (MCF7) and osteosarcoma (HOS) human cancer cell lines was studied. Some of the tested complexes were even several times more cytotoxic as compared with cisplatin employed as a positive control. The improved cytotoxic effect was demonstrated for the platinum(II) complexes 3 (IC50 = 3.2 ± 1.0 μM and 3.2 ± 0.6 μM) and 5 (IC50 = 4.0 ± 1.0 μM and 4.1 ± 1.4 μM) against A2780 and A2780cis, as compared with 11.5 ± 1.6 μM, and 30.3 ± 6.1 μM determined for cisplatin, respectively. The significant in vitro cytotoxicity against MCF7 (IC50 = 8.2 ± 3.8 μM for 12) and A2780 (IC50 = 5.4 ± 1.2 μM for 14) was evaluated for the palladium(II) oxalato complexes, which again exceeded cisplatin, whose IC50 equalled 19.6 ± 4.3 μM against the MCF7 cells. Selected complexes were also screened for their in vitro cytotoxic effect in primary cultures of human hepatocytes and they were found to be non-hepatotoxic. 相似文献
4.
The reaction of the β-diketone 1-phenyl-3-(pyridyn-2-yl)propane-1,3-dione, and the monosubstituted hydrazine 2-hydroxyethylhydrazine has been investigated. Two regioisomers were identified, 2-(3-phenyl-5-(pyridyn-2-yl)-1H-pyrazol-1-yl)ethanol (pzol.1) and 2-(5-phenyl-3-(pyridyn-2-yl)-1H-pyrazol-1-yl)ethanol (pzol.2) in 57:43 ratio. The separation of the regioisomers was done by silica column chromatography using ethyl acetate as eluent.Palladium(II) and platinum(II), [MCl2(pzol.1)2], [MCl2(pzol.2)], and zinc(II), [ZnCl2(pzol.1)], [ZnCl2(pzol.2)] complexes were synthesised and characterised. The crystals and molecular structures of [PdCl2(pzol.2)]·H2O and [ZnCl2(pzol.2)] were solved by X-ray diffraction, and consist of mononuclear complexes. In complex [PdCl2(pzol.2)]·H2O, the Pd(II) centre has a typical square planar geometry, with a slight tetrahedral distortion. The tetra-coordinated atom is bonded to one pyridinic nitrogen, one pyrazolic nitrogen and two chlorine atoms in cis disposition. The pzol.2 ligand acts as a bidentate chelate forming a five-membered metallocycle ring. In complex [ZnCl2(pzol.2)], the Zn(II) is five-coordinated with two Zn-N bonds (Zn-Npz and Zn-Npy), one Zn-OH bond and two Zn-Cl bonds. The coordination geometry is intermediate between a trigonal bipyramid and a square pyramid. In this complex, the ligand pzol.2 is tridentated and forms two metallocycle rings. 相似文献
5.
This report describes the synthesis and structural analysis of stable copper(II) cysteine complexes. Pale pink copper(II) cysteine complexes were synthesized in mole ratios of 1:2, 1:4, and 1:6 of copper(II):cysteine in ethanol. Infrared spectroscopy and X-ray absorption spectroscopy confirmed that copper(II) binding occurred via the thiol ligand of cysteine. XANES analysis showed that the oxidation state of copper remained as copper(II) and the local atomic geometry was similar in all of the cysteine complexes. The EXAFS data indicate that the copper(II) cysteine complexes are forming ring type structures with sulfur ligands from the cysteines acting as bridging ligands. X-ray diffraction revealed that the copper(II) cysteine complexes formed monoclinic cells with maximum crystallinity found in the 1:4 copper(II):cysteine complex. 相似文献
6.
Reaction of the N-alkylaminopyrazole (NN′N) ligands bis[(3,5-dimethyl-1-pyrazolyl)methyl]ethylamine (bdmae) and bis[(3,5-dimethyl-1-pyrazolyl)methyl]isopropylamine (bdmai) with [PdCl2(CH3CN)2] in a 1:1 M/L ratio in CH2Cl2 produces cis-[PdCl2(NN′N)] (NN′N = bdmae (1), bdmai (2)). The solid state structure of complex 1 was determined by X-ray diffraction studies. The bdmae ligand is coordinated through the two Npz atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition.Treatment of the corresponding ligand with [PdCl2(CH3CN)2] in 1:1 M/L ratio in the presence of AgBF4 and metathesis with NaBPh4 in CH2Cl2/CH3OH (3:1) gave [PdCl(bdmae)](BPh4) (3), and in the presence of NaBPh4 in CH2Cl2/CH3CN (3:1) gave [PdCl(bdmai)](BPh4) (4). Complexes 1 and 2 were again obtained when complexes 3 and 4 were heated under reflux in a solution of Et4NCl in acetonitrile. These Pd(II) compounds were characterised by elemental analyses, conductivity measurements, IR, 1H and 13C{1H} NMR, HMQC and NOESY spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed. 相似文献
7.
Christian Tessier 《Inorganica chimica acta》2010,363(11):2652-2660
Pt(II) and Pd(II) compounds containing the free radical 4-aminoTEMPO (4amTEMPO) were synthesized and characterised by X-ray diffraction methods. The disubstituted complexes cis- and trans-Pt(4amTEMPO)2I2 were studied. The trans isomer was prepared from the isomerisation of the cis analogue. The two Pd(II) compounds trans-Pd(4amTEMPO)2X2 (X = Cl and I) were also characterised by crystallographic methods. A mixed-ligand complex cis-Pt(DMSO)(4amTEMPO)Cl2 was synthesized from the isomerisation of the trans isomer in hot water. Its crystal structure was also determined. In all the complexes, the 4amTEMPO ligand is bonded to the metal through the -NH2 group, since the nitroxide O atom is not a good donor atom for the soft Pt(II) and Pd(II) metals. The conformation of the 4-aminoTEMPO ligand was compared to those of the few reported structures in the literature. 相似文献
8.
Urszula Kalinowska Magdalena Ma?ecka Bernhard Lippert 《Inorganica chimica acta》2005,358(8):2464-2472
The synthesis of diethyl (pyridin-2-, -3-, -4-ylmethyl)phosphate (2-pmOpe, 3-pmOpe, 4-pmOpe) ligands and their palladium (II) complexes of general formula trans-[PdCl2L2] (L = 2-pmOpe, 3-pmOpe,4-pmOpe) has been described. Pyridine phosphate derivatives were synthesized via the condensation of phosphorochloridic acid diethyl ester with an appropriate pyridinylmethanol in the presence of triethylamine. The compounds have been identified and characterized by IR, far-IR, 1H NMR, 31P NMR, 31P CP-MAS NMR and elemental analyses. The crystal and molecular structures of palladium (II) complexes, i.e., [PdCl2(2-pmOpe)2] and [PdCl2(4-pmOpe)2] determined by the X-ray diffraction method, are presented. In both structures, Pd(II) ions are four-coordinated by two chlorine atoms and two pyridine nitrogen atoms. The geometry of complexes is square-planar and adopt a trans configuration, which is consistent with preparation method. 相似文献
9.
The first [Pd(Ln)2(ox)] xH2O oxalato(ox) complexes involving 2-chloro-N6-(benzyl)-9-isopropyladenine (L1; complex 1), 2-chloro-N6-(4-methoxybenzyl)-9-isopropyladenine (L2; 2), 2-chloro-N6-(2,3-dimethoxybenzyl)-9-isopropyladenine (L3; 3), 2-chloro-N6-(2,4-dimethoxybenzyl)-9-isopropyladenine (L4; 4), and 2-chloro-N6-(4-methylbenzyl)-9-isopropyladenine (L5; 5) have been synthesized by the reactions of potassium bis(oxalato)palladate(II) dihydrate, [K2Pd(ox)2]·2H2O, with the mentioned organic compounds (H2ox = oxalic acid; x = 0 for 1-3 and 5 or 2 for 4). Elemental analyses (C, H, N), FTIR, Raman and NMR (1H, 13C, 15N) spectroscopies, conductivity measurements and thermal studies (thermogravimetric and differential thermal analyses, TG/DTA) have been used to characterize the prepared complexes. The molecular structures of [Pd(L2)2(ox)] (2) and [Pd(L5)2(ox)]·L5·Me2CO (5·L5·Me2CO) have been determined by a single crystal X-ray analysis. The geometry of these complexes is slightly distorted square-planar with two appropriate Ln (n = 2 or 5) molecules mutually arranged in the head-to-head (2) or head-to-tail (5) orientation. The Ln ligands are coordinated to the central Pd(II) ion via the N7 atoms. The same conclusions regarding the binding properties of L1-L5 ligands can be made based on multinuclear NMR spectra. In vitro cytotoxicity of the complexes 1-5 has been evaluated against human chronic myelogenous leukaemia (K562) and human breast adenocarcinoma (MCF7) cancer cell lines. Significant cytotoxicity has been determined for the complexes 3 (IC50 = 6.2 μM) and 5 (IC50 = 6.8 μM) on the MCF7 cell line, which is even better than that found for the well-known and widely-used platinum-bearing antineoplastic drugs, i.e. oxaliplatin and cisplatin. 相似文献
10.
The coordination behaviour of the title ligand, 5-methyl-3-formylpyrazole N(4)-benzyl-N(4)-methylthiosemicarbazone(HMPz4BM), is reported with solid state isolation of copper(II) complexes, [Cu(HMPz4BM)X2] (X = Cl, Br, NO3, ClO4 and BF4) which have been spectroscopically and structurally characterised. I.r. data for the free ligand and its Cu(II) complexes indicate that HMPz4BM exhibits a neutral NNS tridentate function via the pyrazolyl nitrogen(tertiary), azomethine nitrogen and thione sulphur. Electronic spectral data are suggestive of a square pyramidal environment for the seemingly pentacoordinated Cu(II) species. E.s.r parameters (RT and LNT) of the reported copper(II) complexes are indicative of a dxx2–y2 ground state for the reported species. Cyclic voltammograms of Cu(II) complexes show a quasireversible CuII/CuIII couple and also an irreversible CuII/CuI couple. X-ray crystallography of a representative species, [Cu(HMPz4BM)(NO3)2] (C2/c, monoclinic ), has unambiguously documented the conjectural findings from i.r. data that coordinating sites of the title ligand are pyrazolyl (tertiary)nitrogen, azomethine nitrogen and the thione sulphur (NNS); and the oxygen of one of the nitrate ions has occupied the basal plane; the fifth coordination position has been occupied by the oxygen of another nitrate ion in a square pyramidal geometry. The antibacterial properties of the ligand and its copper(II) complexes studied on microorganism, Staphylococcus aureus have pointed out that most of the complexes have higher activities than that of the free ligand. 相似文献
11.
A new easily synthetic route with a 96% yield of ligand 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethanol (L) is obtained. The reactivity of L against Pd(II), Zn(II) and Cu(II) leads to [PdCl2(L)2] (1), [ZnCl2(L)] (2) and [CuCl(L′)]2 (3) (L′ is the ligand L without alcoholic proton), respectively. According to the different geometries imposed by the metallic centre and the capability of L to present various coordination links, it has been obtained complexes with square planar (1 and 3) or tetrahedral (2) geometry and different nuclearity: monomeric (1 and 2) or dimeric (3). Complete characterisation by analytical and spectroscopic methods, resolution of L and 1-3 by single-crystal X-ray diffraction and magnetic studies for complex 3 are presented. 相似文献
12.
The alkoxo-bridged dinuclear copper(II) complexes [Cu2(ap)2(NO2)2] (1), [Cu2(ap)2(C6H5COO)2] (2) and [Cu2(ap)2μ-1,3-C6H4(COO)2(dmso)2]·dmso (3) (ap = 3-aminopropanolato and dmso = dimethyl sulfoxide) have been synthesized via self-assembly from copper(II) perchlorate, 3-aminopropanol as main chelating ligand and nitrite and isophthalate anions as spacers and benzoate anion as auxiliary ligand. Complexes 1 and 3 crystallize as 2D and 1D coordination polymers, respectively, and their structures consist of dinuclear [Cu2(ap)2]2+ units connected with nitrite and isophthalate ligands. The adjacent dinuclear units of 2 and 1D polymers of 3 are further connected by hydrogen bonds resulting in the formation of 2D layers. The variable temperature crystallographic measurements of 1 at 100, 173 and 293 K indicate the static Jahn-Teller distortion with librational disorder in the nitrite group. Experimental magnetic studies showed that complexes 1-3 exhibit strong antiferromagnetic couplings. The values of the magnetic exchange coupling constant for 1-3 are well reproduced by the theoretical calculations. 相似文献
13.
Michael Carland Teresa Rede Vincent Murray W. David McFadyen 《Inorganica chimica acta》2006,359(10):3252-3256
The complexes dichloro[2-(phenylselanyl)ethanamine]platinum(II), dichloro[2-(benzylselanyl)ethanamine]platinum(II) and dichloro(O-methylselenomethionine)platinum(II) have been prepared and the structure of dichloro(O-methylselenomethionine)platinum(II) has been determined by single crystal X-ray diffraction. The Pt(II) is in a square planar environment and is coordinated by two cis chloride ligands and a chelating O-methylselenomethionine ligand. The cytotoxicities of the compounds have been assessed in the human cell lines HeLa and K562 and they are at least threefold less toxic than cisplatin in both cell lines. 相似文献
14.
Three palladium(II) complexes have been synthesized, using 3,4-bis(cyanamido) cyclobutane-1,2-dione dianion (3,4-bis(cyanamido)squarate or 3,4-NCNsq2−): [Pd(en)(3,4-NCNsq)] · 1.5H2O (1) (en=1,2-diaminoethane), [Pd(en)(3,4-(NC(O)NH2)sq)] · 0.5H2O (2) and K3Na[Pd2(3,4-(NCN)2sq)4] · 5H2O (3). Complex 1 has been characterized by elemental analysis, IR and 13C NMR spectroscopies. Complexes 2 and 3 have been characterized by single-crystal X-ray diffraction. In complex 2, the unusual hydration of the cyanamido ligand was observed, it proceeds in the coordination sphere of the palladium and leads to a chelating urea squarate ligand. Complex 3 is an anionic dinuclear complex containing four bridging cyanamido squarate ligands. In complexes 2 and 3, the 3,4-NCNsq2− ligand (hydrated or not) is, for the first time, coordinated to the metal atom by the two amido nitrogen atoms, either in a chelating mode (complex 2) or in a bridging mode giving a short Pd ? Pd distance of 2.8866(15) Å (complex 3). Electrochemical studies in acetonitrile and dmf solutions have been performed on complexes 1 and 3. 相似文献
15.
Christophe Fliedel 《Inorganica chimica acta》2007,360(1):143-148
A new imidazolinium [(SIBiphen)H](BF4) was synthesized in three steps from 2-aminobiphenyl. The reaction of the salt with Pd(OAc)2, NaI and t-BuOK gave a dimeric Pd(II) complex [(SIBiphen)PdI2]2, which was analyzed by an X-ray diffraction study. The reaction of [Pd(allyl)Cl]2, the imidazolinium salt and t-BuOK in THF at −78 °C gave the monomeric Pd complex, in which the N-heterocyclic carbene was bound to the metal centre, as confirmed by a single-crystal X-ray diffraction study. A preliminary catalytic study showed that these new systems were moderately active in the Suzuki-Miyaura coupling of aryl halides. 相似文献
16.
Susmita Bandyopadhyay G.N. Mukherjee Andrea Cantoni Siddhartha Chaudhuri 《Inorganica chimica acta》2004,357(12):3563-3573
Combined pH-metric, UV-Vis, 1H NMR and EPR spectral investigations on the complex formation of M(II) ions (M=Co, Ni, Cu and Zn) with N-(2-benzimidazolyl)methyliminodiacetic acid (H2bzimida, hereafter H2L) in aqueous solution at a fixed ionic strength, I=10−1 mol dm−3, at 25 ± 1 °C indicate the formation of M(L), M(H−1L)− and M2(H−1L)+ complexes. Proton-ligand and metal-ligand constants and the complex formation equilibria have been elucidated. Solid complexes, [M(L)(H2O)2] · nH2O (n=1 for M = Co and Zn, n=2 for M = Ni) and {Cu (μ-L) · 4H2O}n, have been isolated and characterized by elemental analysis, spectral, conductance and magnetic measurements and thermal studies. Structures of [Ni(L)(H2O)2] · 2H2O and {Cu(μ-L) · 4H2O}n have been determined by single crystal X-ray diffraction. The nickel(II) complex exists in a distorted octahedral environment in which the metal ion is coordinated by the two carboxylate O atoms, the amino-N atom of the iminodiacetate moiety and the pyridine type N-atom of the benzimidazole moiety. Two aqua O atoms function as fifth and sixth donor atoms. The copper(II) complex is made up of interpenetrating polymeric chains of antiferromagnetically coupled Cu(II) ions linked by carboxylato bridges in syn-anti (apical-equatorial) bonding mode and stabilized via interchain hydrogen bonds and π-π stacking interactions. 相似文献
17.
The electrochemical and photophysical properties of two bis-nitrilo ruthenium(II) complexes formulated as [Ru(bpy)2(L)2](PF6)2, where bpy is 2,2′-bipyridine and L is AN = CH3CN and sn = NC-CH2CH2-CN, have been investigated. Electrochemical data are typical of Ru-bpy complexes with two reversible reduction peaks located near −1.3 and −1.6 V assigned to each bipyridine ligand and one RuII/RuIII oxidation wave centered at approximately +1.5 V. The sn derivative is both IR and Raman active with its coordinated CN stretch appearing at 2277 cm−1 and 2273 cm−1, respectively. The UV/Vis absorption spectrum of the sn derivative is dominated by an intense (εmax ∼ 58700 M−1 cm−1) absorption band at 287 nm assigned as a LC (π → π∗) transition. The peak observed at 418 nm (ε ∼ 10 400 M−1 cm−1) is an MLCT band while the one at 244 nm (ε ∼ 23 600 M−1 cm−1) is of LMLCT character. The AN derivative behaves similarly. Both complexes show low-temperature emission at around 537 nm with a lifetime near 10.0 μs. 1H and 13C assignments are consistent with the formulation of the complexes. The complexes undergo photosubstitution of solvent with quantum efficiencies near one. Calculated and experimental results support replacement of the nitrile ligands by solvent. Based on DFT calculations, the electron density of the HOMO lies on the metal center, the bipyridine ligands and the nitrile ligands and electron density of the LUMO resides primarily on the bipyridine ligands. The electronic spectra obtained from TDDFT calculations closely match the experimental ones. 相似文献
18.
Polynuclear self-assembly molecules of general formula [{Pd(en)}x(ligand)y](NO3)2x (A) undergo ligand exchange reaction when heated in DMSO. A mixture of [Pdm(ligand)n](NO3)2m (B) and [Pd(en)2](NO3)2 (C) is generated in this process. The binuclear compound (A) containing a bidentate, non-chelating ligand 1,4-bis(4′-pyridylmethyl)-2,3,5,6-tetrafluorobenzene, is subjected to ligand exchange where upon the compound (A) remains in a dynamic equilibrium with the mixture of ensuing (B) and (C). Combination of separately prepared (B) and (C) also generates (A), thus equilibrium of (A) with (B) and (C) is again observed. We predict [{Pd(bpy)}x(ligand)y](NO3)2x (A′) where 2,2′-bipyridyl (bpy) is the cis-protecting group would not probably undergo ligand exchange. The idea was conceived from the fact that (bpy) is more rigid compared to (en) moreover one of the expected products in the event of ligand exchange [Pd(bpy)2](NO3)2 (C′) is not really very stable unlike (C). In fact, when (A′) is heated in DMSO no ligand exchange is observed at all. More interestingly combination of (B) and (C′) generated (A′) smoothly. Mononuclear complexes obtained from the ligand 4-phenylpyridine are also used for similar study for comparison. It is suggested that (bpy) could serve as a better cis-protecting group for Pd(II)-based self-assembly coordination cage compounds particularly when dissolution of the assemblies in polar solvents and heating of the resultant solution is required. 相似文献
19.
Djenana U. Miodragovi? Dragana M. Miti? Goran A. Bogdanovi? Maja D. Vitorovi? Branislav J. Nastasijevi? Katarina K. An?elkovi? 《Inorganica chimica acta》2008,361(1):86-94
For the first time, complexes of Zn(II), Cd(II) and Co(II) (1-3) with N-benzyloxycarbonylglycine have been synthesized and characterized. The complexes adopt tetrahedral, pentagonal-bipyramidal and octahedral geometry, respectively. The structure of the polymeric cadmium complex was resolved by single crystal X-ray analysis. The cadmium ion has a distorted pentagonal-bipyramidal coordination formed by two water molecules and two N-benzyloxycarbonylglycinato ligands (N-Boc) coordinated in different fashions, one as bidentate and the second connecting three cadmium atoms. In a rather complicated 2D supramolecular structure, the phenyl rings interact mutually exclusively by the CH?π interactions.Investigation of the antimicrobial activity of the obtained complexes and N-benzyloxycarbonylglycine revealed that the ligand does not inhibit the growth of Candida albicans, whereas the newly synthesized complexes suppress the growth of this human fungal pathogen. 相似文献
20.
Ferda Ari Nazlihan Aztopal Ceyda Icsel Veysel T. Yilmaz Emel Guney Orhan Buyukgungor Engin Ulukaya 《Bioorganic & medicinal chemistry》2013,21(21):6427-6434
Four palladium(II) and platinum(II) saccharinate (sac) complexes with 2-(hydroxymethyl)pyridine (2-hmpy) and 2-(2-hydroxyethyl)pyridine (2-hepy), namely trans-[Pd(2-hmpy)2(sac)2]·H2O (1), trans-[Pt(2-hmpy)2(sac)2]·3H2O (2), trans-[Pd(2-hepy)2(sac)2] (3) and trans-[Pt(2-hepy)2(sac)2] (4), have been synthesized and characterized by elemental analysis, UV–vis, IR and NMR. Single crystal X-ray analysis reveals that the metal(II) ions in each complex are coordinated by two sac and two 2-hmpy or 2-hepy ligands with a trans arrangement. Anticancer effects of 1–4 were tested against four different cancer cell lines (A549 and PC3 for lung cancer, C6 for glioblastoma, and Hep3B for liver cancer). Cytotoxicity was first screened by the MTT assay and the results were further confirmed by the ATP assay. The mode of cell death was determined by both histological and biochemical methods. Among the metal complexes, complex 2 resulted in relatively stronger anti-growth effect in a dose-dependent manner (3.13–200 μM), compared to the others, by inducing apoptosis. 相似文献