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1.
The reaction of [Ru2Cl2(μ-Cl)26-p-cymene)2] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-methoxyphenyl)ethan-1-one (HL1) or 2-fluoro-4-hydroxybenzaldehyde (HL2) was studied. The cationic complexes of formula [RuCl(η6-p-cymene)(HL)]+ were isolated as solid chloride and trifluoromethylsulfate (TfO) salts. A study of the solid state and NMR spectra suggests the presence in the material of two isomers that differ in the configuration in the iminic bond, C2=N3, of the coordinated thiosemicarbazone in the triflate salts and only the E isomer in the chloride. An X-ray study of single crystals of the complexes supports this hypothesis. The thiosemicarbazone ligand coordinates with the ruthenium center through the iminic and sulfur atoms to form a five-membered chelate ring. Furthermore, the isolation of single crystals containing the thiosemicarbazonate complex [Ru2(μ-L2)26-p-cymene)2]2+ suggests the easy labilization of the coordinated chloride in the complex. The redox behavior of the ligands and complexes was evaluated by cyclic voltammetry. It seems to be more difficult to oxidize the complex derived from HL1 than HL2. The ability of the complexes to inhibit cell growth against the NCI-H460, A549 and MDA-MB-231 lines was evaluated. The complexes did not show greater potency than cisplatin, although they did have greater efficacy, especially for the complex derived from HL1.  相似文献   

2.
A new series of monoselenoquinone and diselenoquinone π complexes, [(η6p‐cymene)Ru(η4‐C6R4SeE)] (R=H, E=Se ( 6 ); R=CH3, E=Se ( 7 ); R=H, E=O ( 8 )), as well as selenolate π complexes [(η6p‐cymene)Ru(η5‐C6H3R2Se)][SbF6] (R=H ( 9 ); R=CH3 ( 10 )), stabilized by arene ruthenium moieties were prepared in good yields through nucleophilic substitution reactions from dichlorinated‐arene and hydroxymonochlorinated‐arene ruthenium complexes [(η6p‐cymene)Ru(C6R4XCl)][SbF6]2 (R=H, X=Cl ( 1 ); R=CH3, X=Cl ( 2 ); R=H, X=OH ( 3 )) as well as the monochlorinated π complexes [(η6p‐cymene)Ru(η5‐C6H3R2Cl)][SbF6]2 (R=H ( 4 ); R=CH3 ( 5 )). The X‐ray crystallographic structures of two of the compounds, [(η6p‐cymene)Ru(η4‐C6Me4Se2)] ( 7 ) and [(η6p‐cymene)Ru(η4‐C6H4SeO)] ( 8 ), were determined. The structures confirm the identity of the target compounds and ascertain the coordination mode of these unprecedented ruthenium π complexes of selenoquinones. Furthermore, these new compounds display relevant cytotoxic properties towards human ovarian cancer cells.  相似文献   

3.
A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM−C(N-Dipp)2H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM−C(N-Dipp)2}(Ln)] (M=Li, Na, K, Rb, Cs; L=thf, Et2O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh2CH2-C(N-Dipp)2}]6 was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh2CH2-C(N-Dipp)2}]6 metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes.  相似文献   

4.
Metallafuran complexes with a fused five-membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis-[Ru/Os(dppm)2Cl2] (dppm=1,1-bis(diphenylphosphino)methane). A metal–vinylidene-involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium-containing metallafurans, like many phosphonium-functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by RuII and OsII centers.  相似文献   

5.
凡一明  程骏  高亚飞  施敏  邓亮 《化学学报》2018,76(6):445-452
研究了氮上取代基为1-金刚烷基的苯基硼桥联三氮杂环卡宾配体在铁促进的氮气活化转化反应中的应用.通过苯基硼桥联三氮杂环卡宾亚铁氯化物[PhB(AdIm)3FeCl](1)在氮气氛下与KC8反应合成了一价铁分子氮配合物[PhB(AdIm)3Fe(N2)](2).进一步通过2与KC8和18-C-6的反应合成了零价铁分子氮配合物[K(18-C-6)(THF)]-[PhB(AdIm)3Fe(N2)](4).这些配合物均通过核磁共振、紫外吸收光谱、红外光谱、元素分析等表征,其中配合物2和4的结构经单晶X射线衍射表征确定.配合物2和4的N-N伸缩振动频率分别为1928和1807 cm-1,均为同价态铁末端分子氮配合物最低值.在过量KC8和Me3SiCl存在下,配合物1,2和4均可催化N2的还原硅基化反应,生成N(SiMe33.催化体系的TON可达87.  相似文献   

6.
The chiral cationic complex [Ru(η1-OAc)(CO)((R,R)-Skewphos)(phen)]OAc ( 2 R ), isolated from reaction of [Ru(η1-OAc)(η2-OAc)(R,R)-Skewphos)(CO)] ( 1 R ) with phen, reacts with NaOPiv and KSAc affording [RuX(CO)((R,R)-Skewphos)(phen)]Y (X=Y=OPiv 3 R ; X=SAc, Y=OAc 4 R ). The corresponding enantiomers 2 S - 4 S have been obtained from 1 S containing (S,S)-Skewphos. Reaction of 2 R and 2 S with (S)-cysteine and NaPF6 at pH=9 gives the diastereoisomers [Ru((S)-Cys)(CO)(PP)(phen)]PF6 (PP=(R,R)-Skewphos 2 R -Cys; (S,S)-Skewphos 2 S -Cys). The DFT energetic profile for 2 R with (S)-cysteine in H2O indicates that aquo and hydroxo species are involved in formation of 2 R -Cys. The stability of the ruthenium complexes in 0.9 % w/v NaCl solution, PBS and complete DMEM medium, as well as their n-octanol/water partition coefficient (logP), have been evaluated. The chiral complexes show high cytotoxic activity against SW1736, 8505 C, HCT-116 and A549 cell lines with EC50 values of 2.8–0.04 μM. The (R,R)-Skewphos derivatives show higher cytotoxicity compared to their enantiomers, 4 R (EC50=0.04 μM) being 14 times more cytotoxic than 4 S against the anaplastic thyroid cancer 8505 C cell line.  相似文献   

7.
When the [Ru(p-cymene)(μ-Cl)Cl]2 complex is made to react, in dichloromethane, with the following ligands: 2-aminobenzonitrile (2abn), 4-aminobenzonitrile (4abn), 2-aminopyridine (2ampy) and 4-aminopyridine (4ampy), after addition of hexane, the following compounds are obtained: [Ru(p-cymene)Cl2(2abn)] (I), [Ru(p-cymene)Cl2(4abn)] (II), [Ru(p-cymene)Cl2(2ampy] (III) and [Ru(p-cymene)Cl2(μ-(4ampy)] (IV). All the compounds are characterized by elemental analysis of carbon, hydrogen and nitrogen, proton nuclear magnetic resonance, COSY 1H-1H, high-resolution mass spectrometry (ESI), thermogravimetry and single-crystal X-ray diffraction (the crystal structure of III is reported and compared with the closely related literature of II). The cytotoxicity effects of complexes were described for cervical cancer HeLa cells via 3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide (MTT) assay. The results demonstrate a low in vitro anticancer potential of the complexes.  相似文献   

8.
The monoynes [Rc*C[triple bond]CRc*] and [Rc'C[triple bond]CRc'] were obtained in improved yields using [Mo(CO)6]/2-FC6H5OH as a catalyst in the alkyne metathesis of [Rc*C[triple bond]CMe] and [Rc'C[triple bond]CMe], respectively (Rc = ruthenocenyl, Rc* = 1',2',3',4',5'-pentamethylruthenocenyl, and Rc' = 2',3',4',5'-tetramethylruthenocenyl groups). The diynes [Rc*(C[triple bond]C)2Rc*] and [Rc'(C[triple bond]C)2Rc'] were synthesized by the oxidative coupling of the corresponding terminal ethynes in good yields. The triyne [Rc*(C[triple bond]C)3Rc*] and the tetrayne [Rc*(C[triple bond]C)4Rc*] were prepared by the hetero- and homocoupling of [Rc*C[triple bond]CC[triple bond]CH], which was obtained from the reaction of [Rc*C[triple bond]CCHO] with Li[N2CSiMe3], respectively. Although the oxidation waves did not always exhibit a clear two-electron oxidation process, the oxidation potentials shifted to a lower potential with an increase in the number of methyl substituents on the ruthenocenyl ring, and shifted to a higher potential with the increase in the number of C[triple bond]C units; this result is in contrast to that found in the [Rc(CH=CH)(n)Rc] series. The chemical oxidation of [Rc'C[triple bond]CRc'] yielded a stable two-electron-oxidized species, the structure of which was confirmed by X-ray crystallography to be [Ru2(mu2-eta(6):eta(6)-C5Me4C=CC5Me4)(eta-C5H5)2](BF4)2. Changing the substituents (Rc, Rc*, and Rc') had no effect on the chemical oxidation, but in the case of the Rc' series the Me substituent increased the stability of the two-electron-oxidized species in solution. The diyne [Rc*(C[triple bond]C)2Rc*] and the triyne [Rc*(C[triple bond]C)3Rc*] also gave a similar but unstable two-electron-oxidized species. In acetone or acetonitrile, the two-electron-oxidized species of [Rc*C[triple bond]CRc*] and [Rc*(C[triple bond]C)2Rc*] gradually formed the corresponding bis(fulvene)-type complexes. This implies that the two-electron-oxidized species of [Rc*(C[triple bond]C)(n)Rc*] are destabilized with the increasing n.  相似文献   

9.
Zn(II) complexes bearing tris[3-(2-pyridyl)-pyrazolyl] borate (Tppy) ligand (1–3) was synthesized and examined by spectroscopic and analytical tools. Mononuclear [TppyZnCl] (1) has a Zn(II) centre with one arm (pyrazolyl-pyridyl) dangling outside the coordination sphere which is a novel finding in TppyZn(II) chemistry. In complex [TppyZn(H2O)][BF4] (2) hydrogen bonding interaction of aqua moiety stabilizes the dangling arm. In addition, solution state behaviour of complex 1 confirms the tridentate binding mode and reactivity studies show the exogenous axial substituents used to form the [TppyZnN3] (3). The complexes (1–3) were tested for their ability to bind with Calf thymus (CT) DNA and Bovine serum albumin (BSA) wherein they revealed to exhibit good binding constant values with both the biomolecules in the order of 104–105 M−1. The intercalative binding mode with CT DNA was confirmed from the UV-Visible absorption, viscosity, and ethidium bromide (EB) DNA displacement studies. Further, the complexes were tested for in vitro cytotoxic ability on four triple-negative breast cancer (TNBC) cell lines (MDA-MB-231, MDA-MB-468, HCC1937, and Hs 578T). All three complexes (1–3) exhibited good IC50 values (6.81 to 16.87 μM for 24 h as seen from the MTS assay) results which indicated that these complexes were found to be potential anticancer agents against the TNBC cells.  相似文献   

10.
We have developed six dihydroxidoplatinum(IV) compounds with cytotoxic potential. Each derived from active platinum(II) species, these complexes consist of a heterocyclic ligand (HL) and ancillary ligand (AL) in the form [Pt(HL)(AL)(OH)2]2+, where HL is a methyl‐functionalised variant of 1,10‐phenanthroline and AL is the S,S or R,R isomer of 1,2‐diaminocyclohexane. NMR characterisation and X‐ray diffraction studies clearly confirmed the coordination geometry of the octahedral platinum(IV) complexes. The self‐stacking of these complexes was determined using pulsed gradient stimulated echo nuclear magnetic resonance. The self‐association behaviour of square planar platinum(II) complexes is largely dependent on concentration, whereas platinum(IV) complexes do not aggregate under the same conditions, possibly due to the presence of axial ligands. The cytotoxicity of the most active complex, exhibited in several cell lines, has been retained in the platinum(IV) form.  相似文献   

11.
12.
本工作设计合成了6种新型混胺羧酸根合铂(Ⅱ)类配合物[Pt((?)NH)(NH3)X2](a~f){其中,X=CH3COO-(乙酸根),CH3Cl COO-(氯乙酸根),CHCl2COO-(二氯乙酸根),C6H5-COO-(苯甲酸根),p-CH3-C6H4-COO-(对甲基苯甲酸根),p-CH3O-C6H4-COO-(对甲氧基苯甲酸根)}。通过元素分析、摩尔电导、差热分析、红外光谱、紫外光谱和 1H核磁共振谱对配合物进行了表征。通过MTT法研究了配合物的体外抗肿瘤活性,通过等离子体质谱研究了配合物与细胞DNA的键合量;体外抗肿瘤活性测试表明,配合物(a~f)对所测试的肿瘤细胞MCF-7、HCT-8和BGC-823没有表现出活性,但对EJ和HL-60两种肿瘤细胞表现出好的活性,而且配合物(d~f)对HL-60细胞的活性与顺铂相当。配合物(a~f)与HL-60细胞的DNA键合量与其作用浓度表现出一定的依赖性,从小到大的顺序为:cisplatin < c < b < a < f < e < d。  相似文献   

13.
In quest of antimicrobial and anticancer agents, metformin containing Ni (II) complexes, [Ni (Met)2]Cl·OH ( 1 ) and [Ni (Met)(IDA)] ( 2 ) {Met: metformin, IDA: iminodiacetic acid} were synthesized and X-ray structure of 1 is four-coordinate square planar geometry. Bovine serum albumin (BSA) interaction and binding studies to Met, IDA and their Ni (II) complexes were investigated and showed a strong interaction. A static quenching process was proposed at low concentrations of compounds whereas, combined quenching process was observed for 1 and 2 at higher concentrations. Kinetic stability, affinity and association constants of compounds-BSA were studied using stopped-flow technique and a mechanism was proposed: a fast and reversible step of BSA binding including complex formation and dissociation was proposed; for the second step, a reversible reaction was observed for 1 and 2 whereas, an irreversible reaction with Met and IDA was observed indicating that coordination with nickel ions change the interaction mechanism. Additionally, the antibacterial investigation against both Gram-positive and Gram-negative bacteria showed that all compounds exhibited significant activities. They also show cytotoxicity against HepG2 human liver cancer cell but the half maximal inhibitory concentration (IC50) values obtained for the cell lines were higher in comparison with cisplatin. Although Met-BSA and IDA-BSA are kinetically more stable than that of 1 -BSA and 2 -BSA, 1 -BSA and 2 -BSA showed better antibacterial and cytotoxic activities which is in agreement with the binding constants.  相似文献   

14.
15.
Two new bichromophoric ruthenium(II) complexes, [Ru(bpy)2(bpy‐CM)](PF6)2 and [Ru(bpy)2(bpy‐CM343)](PF6)2 (bpy=2,2′‐bipyridine, CM=coumarin) with appended coumarin ligands have been designed and synthesized. The energy‐transfer‐based sensing of esterase by the complexes has been studied by using UV/Vis and luminescence spectroscopic methods. The cytotoxicity and the cellular uptake of one of the complexes have also been investigated.  相似文献   

16.
The reaction of [CpRuCl(PPh3)2] (Cp=cyclopentadienyl) and [CpRuCl(dppe)] (dppe=Ph2PCH2CH2PPh2) with bis‐ and tris‐phosphine ligands 1,4‐(Ph2PC≡C)2C6H4 ( 1 ) and 1,3,5‐(Ph2PC≡C)3C6H3 ( 2 ), prepared by Ni‐catalysed cross‐coupling reactions between terminal alkynes and diphenylchlorophosphine, has been investigated. Using metal‐directed self‐assembly methodologies, two linear bimetallic complexes, [{CpRuCl(PPh3)}2(μ‐dppab)] ( 3 ) and [{CpRu(dppe)}2(μ‐dppab)](PF6)2 ( 4 ), and the mononuclear complex [CpRuCl(PPh3)(η1‐dppab)] ( 6 ), which contains a “dangling arm” ligand, were prepared (dppab=1,4‐bis[(diphenylphosphino)ethynyl]benzene). Moreover, by using the triphosphine 1,3,5‐tris[(diphenylphosphino)ethynyl]benzene (tppab), the trimetallic [{CpRuCl(PPh3)}33‐tppab)] ( 5 ) species was synthesised, which is the first example of a chiral‐at‐ruthenium complex containing three different stereogenic centres. Besides these open‐chain complexes, the neutral cyclic species [{CpRuCl(μ‐dppab)}2] ( 7 ) was also obtained under different experimental conditions. The coordination chemistry of such systems towards supramolecular assemblies was tested by reaction of the bimetallic precursor 3 with additional equivalents of ligand 2 . Two rigid macrocycles based on cis coordination of dppab to [CpRu(PPh3)] were obtained, that is, the dinuclear complex [{CpRu(PPh3)(μ‐dppab)}2](PF6)2 ( 8 ) and the tetranuclear square [{CpRu(PPh3)(μ‐dppab)}4](PF6)4 ( 9 ). The solid‐state structures of 7 and 8 have been determined by X‐ray diffraction analysis and show a different arrangement of the two parallel dppab ligands. All compounds were characterised by various methods including ESIMS, electrochemistry and by X‐band ESR spectroscopy in the case of the electrogenerated paramagnetic species.  相似文献   

17.
Copper plays an important role in alkyne coordination chemistry and transformations. This report describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support. Details of the related copper(I) complex of HC≡CSiMe3 are also reported. They are three-coordinate copper complexes featuring η2-bound alkynes. Raman data show significant red-shifts in C≡C stretch of [H2B(3,5-(CF3)2Pz)2]Cu(HC≡CH) and [H2B(3,5-(CF3)2Pz)2]Cu(HC≡CSiMe3) relative to those of the corresponding alkynes. Computational analysis using DFT indicates that the Cu(I) alkyne interaction in these molecules is primarily of the electrostatic character. The π-backbonding is the larger component of the orbital contribution to the interaction. The dinuclear complexes such as Cu2(μ-[3,5-(CF3)2Pz])2(HC≡CH)2 display similar Cu-alkyne bonding features. The mononuclear [H2B(3,5-(CF3)2Pz)2]Cu(NCMe) complex catalyzes [3 + 2] cycloadditions between tolyl azide and a variety of alkynes including acetylene. It is comparatively less effective than the related trinuclear copper catalyst {μ-[3,5-(CF3)2Pz]Cu}3 involving bridging pyrazolates.  相似文献   

18.
Complexes of the type [Pt R2 (dppma-PP′)] (R─Me, Et, Ph, CH2Ph, C6H4 Me-p, C6H4OMe-2, CH2CMe3, 1-naphthyl, C6H4Me-o, dppma = Ph2PNMe PPh2) have been prepared from [PtCl2, (dppma-PP′)] and the corresponding alkyl-lithium or Grignard reagents. Equilibrium constants, k, for the conversion of [PtR2 (dppma-PP′)] into cis-[PtR2(dppma-P)2] with dppma were studied using 31P NMR spectroscopy at room temperature. Equilibrium is rapidly established for R─C6H4-Me-o, at 20°C. Complex of the type cis-[PtR2 (dppma-P)2] was isolated R─C6H4 Me-o. The complexes [PtMe2(dppma-P)2] and [Pt(o-methoxyphenyl)2(dppma-P)2] were prepared, but unfortunately decomposed once isolated, the only evidence for its formation being from 31P-{1H} NMZR spectroscopy. The o-tolyl or 1-naphthyl complexes exist as syn-anti mixtures in solution, due to restricted rotation around the platinum aryl bonds. Treatment of several complexes of the type [PtR2(dppma-PP′)] with MeI gives [PtR2Me(I)(dppma-PP′)] with trans addition of MeI. Treatment of [PtR2(dppma-PP′)] with HCl gives [Pt Cl (R) (dppma-PP′)] for R─C6H2Me3-2,4,6, C6H4-CH3-2, C6H4-Me-4, Me, 1-naphthyl. The 1H, 31P NMR parameters for these complexes are discussed. Attempted preparation of complexes of the type [PtR2 (dppma-P)2M] (R─C6H4-Me-2, Me CN-C6H4-Me-4); M─Pd, Pt, Au,) are reported.  相似文献   

19.
本文通过异氰酸酰化反应合成了含有脲基的苯乙炔新型配体及以它作为辅助配体的4′-(对甲基苯基)-6-苯基-2,2′-二联吡啶铂(II)络合物,初步研究了铂(II)络合物的光物理性质,发现由于脲基的存在,当浓度大于3.32×10-5mol/L时铂(II)络合物能够发生分子间簇集.  相似文献   

20.
IntroductionDye sensitizedsolarcells (DSSC)havebecomethefocusofmanyinvestigationssinceMichaelGr tzelandco workersmadethedyemoleculesadsorbedonaporousnet workoftheinterconnectednanometer sizedcrystallinesofawidebandgapsemiconductor.1 3Animpressivesolar to electricalenergyconversionefficiencyof 10 %hasbeenre portedanditmakespracticalapplicationfeasible .4 Thissystemconsistsofadye coatedsemiconductorelectrodeandacounterelectrodearrangedinasandwichconfigura tionandtheinter electrodespaceisfilled…  相似文献   

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