首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Reaction of 3-pyridinehydroxamic acid and 4-pyridinehydroxamic acid (3-pyha and 4-pyha) with either [NBu4][RuCl4(dmso-S)2] or [(dmso)2H][RuCl4(dmso-S)2] (dmso is dimethyl sulfoxide) in acetone afforded three new ruthenium(III) dimethyl sulfoxide pyridinehydroxamic acid complexes: [NBu4][trans-RuCl4(dmso-S)(4-pyha)]·CH3COCH3 (1), [3-pyhaH][trans-RuCl4(dmso-S)(3-pyha)] (2) and [4-pyhaH][trans-RuCl4(dmso-S)(4-pyha)] (3). The solid-state structure of [NBu4][trans-RuCl4(dmso-S)(4-pyha)]·CH3COCH3 (1) was determined by X-ray crystallography. 2 and 3 were pharmacologically evaluated for their in vitro cytotoxicity, their ability to inhibit cell invasion and their gelatinase activity. 2 and 3 were devoid of cytotoxicity against the cell lines tested. 2 inhibited invasion of the highly invasive MDA-MB-231 cells to a much greater extent than 3. Contrary to expectations, neither 2 nor 3 had any inhibitory effect on matrix metalloproteinase (MMP) production and/or activity and in fact 3 was found to enhance the production and/or activity of both MMP-2 and MMP-9.  相似文献   

2.
This work reports on the bimolecular sensitization of nitric oxide release from cis-[Ru(bpy)2(iso)NO](PF6)3 (1) (iso = isoquinoline and bpy = 2,2′-bipyridine) by irradiating the MLCT transition of the chloro analog cis-[Ru(bpy)2(iso)Cl]PF6 (2). The compounds displayed peaks in the ESI-MS spectra at m/z 749.1 and m/z 578.1 ascribed, respectively, to ([1(NO0)−2PF6·CH3OH]2+) and ([2−PF6]+). In the cyclic voltammograms, the nitrosyl complex presented two redox waves related to the NO ligand at 0.48 and −0.37 V (versus Ag/AgCl, NO+/0/−1 processes), while the sensitizer showed two reversible waves at 0.79 and −1.46 V (versus Ag/AgCl, Ru2+/3+ and bpy 0/−1, respectively). The most important feature of this system is that the nitrosyl compound does not have significant absorption in the visible region, while the sensitizer has an intense band centered at 496 nm. The irradiation of an equimolar mixture of the two compounds in an ethanol:water solution (v:v) with light of λ > 500 nm leads to NO release, as probed by amperometric measurements. The variational method was applied, showing that the two compounds self-assembly in solution with a 1:1 stoichiometry. Fluorescence spectra acquired at 77 K provided the E0-0 for the system and, from the thermodynamic cycle it was estimated that the photoinduced electron transfer between the species has a ΔG value of −1.59 eV.  相似文献   

3.
The reaction of [RuCl3(2mqn)NO] (H2mqn=2-methyl-8-quinolinol) with 2-chloro-8-quinolinol (H2cqn) afforded cis-1 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2cqn is trans to the NO) (complex 1), cis-1 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2mqn is trans to the NO) (complex 2) and a 1:1 mixture of cis-2 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2mqn is trans to the NO) and cis-2 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2cqn is trans to the NO) (complex 3). The reaction was compared with that of [RuCl3(2mqn)NO] with 8-quinolinol (Hqn) or 5-chloro-8-quinolinol (H5cqn). Photoirradiation reaction of complex 1 at room temperature in deaerated CH2Cl2 in the presence of NO gave trans-[RuCl(2cqn)(2mqn)NO] (the Cl is trans to the NO) and complex 2 with recovery of complex 1. The reaction was contrasted with that of cis-1 [RuCl(qn)(2mqn)NO] or cis-1 [RuCl(5cqn)(2mqn)NO]. The crystal structure of complex 1 was determined by X-ray diffraction. The reactions were examined under consideration of atomic charge of the phenolato oxygen in 8-quinolinol and its derivatives calculated at the restricted Hartree-Fock/6-311G** level.  相似文献   

4.
Preliminary pharmacological studies of various nitric oxide (NO) photo-releasing agents are reported based on the flash-photolysis studies of the nitro ruthenium complexes cis-[RuII(NO2)L(bpy)2]+ (bpy = 2,2′-bipyridine and L = pyridine, 4-picoline and pyrazine) and [RuII(NO2)(bpy)(terpy)]+ (terpy = terpyridine) in physiological medium. The net photoreactions under these conditions are two primary photoproducts, in (I) there is RuII-NO2 photoaquation, where the photoproducts are RuII-H2O plus and (II) homolytic dissociation of NO from a coordinated nitrito to derive the RuII-OH2 specie and NO. Based on photochemical processes, the nitro ruthenium complexes were incorporated in water in oil (W/O) microemulsion and used in the vasorelaxation induced experiment. Denuded rat aortas were contracted with KCl and nitro ruthenium complexes in microemulsion were added. Perfusion pressures were recorded while arteries were irradiated at 355 nm The time to reach maximum relaxation was longer for [RuII(NO2)(bpy)(terpy)]+ complex (ca. 50 min, n = 6) than for cis-[Ru(NO2)L(bpy)2]+ with L = py and 4-pic complex (ca. 28 min, n = 6) and cis-[Ru(NO2)(bpy)2 (pz)]2+ complex (ca. 24 min, n = 5).  相似文献   

5.
Subsequent addition of 1,2-benzenedithiol (S2-H2) and nBuLi to a solution of [Ru(NO)Cl3 · xMeOH] in THF afforded exclusively the monomeric species NBu4[RuII(NO)(S2)2] (1). Formation of dimeric (NBu4)2[RuII(NO)(S2)2]2 (2) has been confirmed when the deprotonated ligand S2-Li2 was added to [Ru(NO)Cl3 · xMeOH] and allowed to stir for 30 h. The monomer 1 undergoes aerial oxidation to give (NBu4)2[RuIV(S2)3] (3). The reaction between RuCl3 · xH2O and S2-H2 in the presence of NaOMe, afforded the dinulear RuIII species (NMe4)2[RuIII(S2)2]2 (4). A modified method for the preparation of 1 is being employed to synthesize the osmium analogue NBu4[Os(NO)(S2)2] (5) effectively. The solid state structures of 1, 2 and 3 were determined by X-ray crystal structure analysis. A comparison of relevant bond distance data suggests that 1,2-benzenedithiolate acts as an “innocent” ligand.  相似文献   

6.
The nitrosyl complex H[TcNOCl4] reacts with the tridentate ligand bis[(2-diphenylphosphino)propyl]amine (PNPpr) to yield a mixture of the mer or fac isomers of [TcCl2(NO)(PNPpr)]. In acetonitrile, where the ligand is freely soluble, reaction occurs at room temperature to yield mostly the mer isomer with the linear nitrosyl ligand cis to the amine ligand; and the phosphine ligands arranged in a mutually trans orientation. The reaction in methanol requires reflux to dissolve the lipophilic ligand and generates the fac isomer of [TcCl2(NO)(PNPpr)] as the major product, with the tridentate ligand in a facial arrangement, leaving the chlorides and nitrosyl ligand in the remaining facial sites. The steric bulk of the tridentate ligand’s diphenylphophino-moieties results in a significant distortion from octahedral geometry, with the P-Tc-P bond angle expanded to 99.48(4)°.The infrared spectra display absorptions from these nitrosyl ligands in the 1700 and 1800 cm−1 regions for the fac and mer isomers, respectively. The ESI(+) mass spectra each display the parent ion at 647 m/z.  相似文献   

7.
The 16-electron, coordinatively unsaturated, dicationic ruthenium complex [Ru(P(OH)2(OMe))(dppe)2][OTf]2 (1a) brings about the heterolysis of the C-H bond in phenylacetylene to afford the phenylacetylide complex trans-[Ru(CCPh)(P(OH)2(OMe))(dppe)2][OTf] (2). The phenylacetylide complex undergoes hydrogenation to give a ruthenium hydride complex trans-[Ru(H)(P(OH)2(OMe))(dppe)2][OTf] (3) and phenylacetylene via the addition of H2 across the Ru-C bond. The 16-electron complex also reacts with HSiCl3 quite vigorously to yield a chloride complex trans-[Ru(Cl)(P(OH)2(OMe))(dppe)2][OTf] (4). On the other hand, the other coordinatively unsaturated ruthenium complex [Ru(P(OH)3)(dppe)2][OTf]2 (1b) reacts with a base N-benzylideneaniline to afford a phosphonate complex [Ru(P(O)(OH)2)(dppe)2][OTf] (5) via the abstraction of one of the protons of the P(OH)3 ligand by the base. The phenylacetylide, chloride, and the phosphonate complexes have been structurally characterized. The phosphonate complex reacts with H2 to afford the corresponding dihydrogen complex trans-[Ru(η2-H2)(P(O)(OH)2)(dppe)2][OTf] (5-H2). The intact nature of the H-H bond in this species was established using variable temperature 1H spin-lattice relaxation time measurements and the observation of a significant J(H,D) coupling in the HD isotopomer trans-[Ru(η2-HD)(P(O)(OH)2)(dppe)2][OTf] (5-HD).  相似文献   

8.
The hydroxo complex [NBu4]2[Ni2(C6F5)4(μ-OH)2] reacts with ammonium O,O-dialkyldithiophosphates, O-alkyl-p-methoxyphenyldithiophosphonate acids and ammonium O-alkylferrocenyldithiophosphonates in dichloromethane under mild conditions to give, respectively, [NBu4][Ni(C6F5)2{S(S)P(OR)2}] (R=Me (1), Et (2), iPr (3)) and [NBu4][Ni(C6F5)2{S(S)P(OR)Ar}] (Ar=p-MeOC6H4, R=Me (4), Et (5), iPr (6); Ar=ferrocenyl; R=Me (7), Et (8), iPr (9)). The monothiophosphonate nickel complexes [NBu4][Ni(C6F5)2{S(S)P(OR)(ferrocenyl)}] (R=Et (10), iPr (11)) are obtained by reaction of the hydroxo complex with O-alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, 1H, 19F and 31P NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of [NBu4][Ni(C6F5)2{S(S)P(OMe)(p-MeOC6H4)}] (4) and [NBu4][Ni(C6F5)2{S(O)P(OEt)(ferrocenyl)}] (10) shows that in both cases the coordination around the nickel atom es essentially square planar with NiC2S2 and NiC2SO central cores, respectively.  相似文献   

9.
We have prepared the oxo-bridged dimer [Ru(bpb)(NO]2(μ-O) in 60% isolated yield from the reaction of the known Ru(bpb)(NO)Cl with silver nitrite. The compound exhibits a υNO of 1758 cm−1 (KBr pellet). The crystal structure reveals a linear ON-Ru-O-Ru-NO fragment with the oxo atom serving as an inversion center in the molecule. The redox behavior in DMF is characterized by a reversible reduction followed by a second but irreversible reduction in this solvent.  相似文献   

10.
The photochemical and pharmacological studies of the novel [Ru(L)(tpy)NO]3+ L = bpy (2,2′-bipyridine), NH · NHq (quinonediimine) and NH2.NH2cat (o-phenylenediamine) were investigated in aqueous medium. The synthesized nitrosyl ruthenium complexes showed nitric oxide (NO) release under light irradiation at 355 nm for [Ru(L)(tpy)NO]3+ complex with quantum yield of 0.14 ± 0.02, 0.47 ± 0.03 and 0.46 ± 0.02 mol Einstein−1 for L = bpy, NH · NHq and NH2 · NH2cat, respectively, and 0.0065 ± 0.001 mol Einstein−1 for light irradiation at 532 nm for [Ru(NH · NHq)(tpy)NO]3+ complex. The photochemical pathway at 355 nm light irradiation was described as a multi-step mechanism, although at 532 nm it was better attributed to a photo-induced electron transfer. The vasorelaxation induced by NO release produced by light irradiation in visible region from physiological solution of [Ru(NH · NHq)(tpy)NO]3+ complex was evaluated and compared with sodium nitroprusside (SNP). The results showed very similar vasodilator power between both species.  相似文献   

11.
Nitric oxide plays an important role in various biological processes, such as neurotransmission, blood pressure control, immunological responses, and antioxidant action. The control of its local concentration, which is crucial for obtaining the desired effect, can be achieved with exogenous NO-carriers. Coordination compounds, in particular ruthenium(III) and (II) amines, are good NO-captors and -deliverers. The chemical and photochemical properties of several ruthenium amine complexes as NO-carriers in vitro and in vivo have been reviewed. These nitrosyl complexes can stimulate mice hippocampus slices, promote the lowering of blood pressure in several in vitro and in vivo models, and control Trypanosoma cruzi and Leishmania major infections, and they are also effective against tumor cells in different models of cancer. These complexes can be activated chemically or photochemically, and the observed biological effects can be attributed to the presence of NO in the compound. Their efficiencies are explained on the basis of the [RuIINO+]3+/[RuIINO0]2+ reduction potential, the specific rate constant for NO liberation from the [RuNO]2+ moiety, and the quantum yield of NO release.  相似文献   

12.
Treatment of [H(TMSO)][trans-RuCl4(TMSO)2] (1) with 2,2′-bipyridine (bpy) in ethanol at room temperature resulted an unknown mer-[RuCl3(TMSO)(bpy)] (3) and a known cis-[RuCl2(TMSO)4] (4) (TMSO =  tetramethylene sulfoxide) complexes. The 3 was obtained by the substitution with bpy in mer-[RuCl3(TMSO)3] (2), whereas 4 was obtained by one-electron reduction of 2, suggesting that 2 is a precursor for both 3 and 4. The structure of 3 was determined by single crystal X-ray diffraction. The reaction is a new synthetic procedure for 3 and/or 3 and 4 in mild reaction conditions from the anionic complex 1. It involves simultaneous substitution and redox reaction. This is the first known example of precisely characterized Ru(III)-chloride-TMSO-bpy-complex derived from anionic [H(TMSO)][trans-RuCl4(TMSO)2] at room temperature.  相似文献   

13.
The photochemical behavior of a series of trans-[Ru(NH3)4L(NO)]3+ complexes, where L=nitrogen bound imidazole, L-histidine, 4-picoline, pyridine, nicotinamide, pyrazine, 4-acetylpyridine, or triethylphosphite is reported. In addition to ligand localized absorption bands (<300 nm), the electronic spectra of these complexes are dominated by relatively low intensity bands assigned as ligand field (LF) and metal to ligand (dπ → NO) charge transfer (MLCT) transitions. Irradiation of aqueous solutions of these complexes with near-UV light (300-370 nm) labilizes NO, i.e.,
  相似文献   

14.
Nitric oxide (NO) has a critical role in several physiological and pathophysiological processes. In this paper, the reactions of the nitrosyl complexes of [Ru(bpy)2L(NO)]n+ type, where L = SO32− and imidazole and bpy = 2,2′-bipiridine, with cysteine and glutathione were studied. The reactions with cysteine and glutathione occurred through the formation of two sequential intermediates, previously described elsewhere, [Ru(bpy)2L(NOSR)]n+ and [Ru(bpy)2L(NOSR)2] (SR = thiol) leading to the final products [Ru(bpy)2L(H2O)]n+ and free NO. The second order rate constant for the second step of this reaction was calculated for cysteine k2(SR) = (2.20 ± 0.12) × 109 M− 1 s− 1 and k2(RSH) = (154 ± 2) M− 1 s− 1 for L = SO32− and k2(SR) = (1.30 ± 0.23) × 109 M− 1 s− 1 and k2(RSH) = (0.84 ± 0.02) M− 1 s− 1 for L = imidazole; while for glutathione they were k2(SR) = (6.70 ± 0.32) × 108 M− 1 s− 1 and k2(RSH) = 11.8 ± 0.3 M− 1 s− 1 for L = SO32− and k2(SR) = (2.50 ± 0.36) × 108 M− 1 s− 1 and k2(RSH) = 0.32 ± 0.01 M− 1 s− 1 for L = imidazole. In all reactions it was possible to detect the release of NO from the complexes, which it is remarkably distinct from other ruthenium metallocompounds described elsewhere with just N2O production. These results shine light on the possible key role of NO release mediated by physiological thiols in reaction with these metallonitrosyl ruthenium complexes.  相似文献   

15.
The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl64? and Ru2OCl104?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl3 per molecule of the complex. All three compounds crystallize in the monoclinic space group P21/n with unit cell dimensions as follows: Cis-OsCl2(dppm)2·CHCl3: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) Å3, Z = 4. cis-RuCl2(dppm)2·CHCl3: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) Å3, Z = 4. trans-RuCl2(dppm)2: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) Å3; Z = 2. The structures were refined to R = 0.044 (Rw = 0.055) for cis-OsCl2(dppm)2·CHCl3; R = 0.065 (Rw = 0.079) for cis-RuCl2(dppm)2·CHCl3 and R = 0.028 (Rw = 0.038) for trans-RuCl2(dppm)2. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.  相似文献   

16.
Abstract

DNA groove binders have been poorly studied as compared to the intercalators. A novel Ru(II) complex of [Ru(aeip)2(Haip)](PF6)2 {Haip?=?2-(9-anthryl)-1H-imidazo[4,5-f][1,10]phenanthroline and aeip = 2-(anthracen-9-yl)-1-ethyl-imidazo[4,5-f][1, 10]phenanthroline} is synthesized and characterized by elemental analysis, 1H NMR spectroscopy and mass spectrometry. The complex is evidenced to be a calf-thymus DNA groove binder with a large intrinsic binding constant of 106 M?1 order of magnitude as supported by UV–visible absorption spectral titrations, salt effects, DNA competitive binding with ethidium bromide, DNA melting experiment, DNA viscosity measurements and density functional theory calculations. The acid-base properties of the complex studied by UV–Vis spectrophotometric titrations are reported as well.  相似文献   

17.
The spectroscopic and photophysical properties of a synthetically versatile ruthenium complex [Ru(bpy)2(LH2)]2+ where LH2 is 2-(4-carboxyphenyl)imidazo[4,5-f][1,10]phenanthroline and bpy is 2,2-bipyridyl and its analogue, [Ru(bpy)2(LOMe)]2+ where the carboxyphenyl functionality is methylated are reported. Both complexes exhibit long-lived luminescence which for [Ru(bpy)2(LH2)]2+ is remarkably enhanced in aqueous compared to organic media. The pH dependence of the electronic absorption and emission spectra in water and acetonitrile are described and the influence of the protonation state of the 2-(4-carboxyphenyl)imidazo[4,5-f][1,10]phenanthroline ligand on the electronic structure of [Ru(bpy)2(LH2)]2+ is discussed. Oxidative quenching of the excited state of the complex by anthraquinone-2-carboxylic acid is investigated for both complexes. In polar media, this is a dynamic process suggesting that the quenching rate is controlled by bimolecular collision with a quenching rate constant, kq, of approximately 6.7 × 109 M−1 s−1 for [Ru(bpy)2(LH2)]2+. In contrast in aprotic solvent, dichloromethane, quenching occurs through a purely static mechanism indicating association between the luminophore and quencher, most likely through hydrogen bonding, between the carboxylic acid moieties of the ruthenium complex and the anthraquinone carboxylic derivative. The association constant for formation of the dyad was determined to be 565 L mol−1 in dichloromethane and the rate of electron transfer was estimated to be 4.7 × 107 s−1. By contrast, for the analogous complex in which the carboxylate is methyl protected mixed static and dynamic quenching behaviour in aprotic solvent.  相似文献   

18.
The design, synthesis, and characterization of an unsymmetrical diamidato-dithiol ligand (H4 1, where the hydrogen atoms represent deprotonatable amide and thiol protons) and its cobalt(III) complex, a synthetic analogue of the cobalt-containing nitrile hydratase enzyme family, are reported. The ligand was prepared in 24% yield from an overall eight-step synthetic pathway following a modified protocol established in our laboratory that includes two peptide couples using O-(1H-benzotriazol-1-yl)-N,N,N??N??tetramethyluronium hexafluorophosphate as the coupling agent. The ligand and all precursors were characterized by NMR spectroscopy and elemental analysis. The cobalt nitrile hydratase synthetic analogue complex [NBu4][Co(1)] was prepared on deprotonating ligand H4 1 to [1]4??/sup> on addition of 5?equiv of NaH in N,N-dimethylformamide and adding 1?equiv of CoCl2 at ??0?°C under a N2 atmosphere followed by oxidizing the complex by stirring it overnight open to dry air. The complex [NBu4][Co(1)] was isolated after counterion exchange with 1?equiv of NBu4Cl followed by crystallization from MeCN/Et2O in 71% yield. The structure of the complex was confirmed by X-ray diffraction analysis. Cyclic voltammetry studies on [NBu4][Co(1)] in a 0.1?M [NBu4][PF6]/MeCN solution showed a quasi-reversible reduction potential at ??.1?V (vs. Ag/AgCl), and magnetic susceptibility investigations indicated the complex is paramagnetic in both the solid and the solution states as determined from inverse-Gouy and Evans NMR methods, respectively.  相似文献   

19.
A theoretical study of the ruthenium(III) complex [RuCl2(pz2CHSO3)(en)] and of its nitrosyl-substituted product [Ru(NO)Cl(pz2CHSO3)(en)]+ is presented, based on density functional calculations. Several isomers of each compound differing in the position of the anionic tail of a bis(3,4-dimethyl-1-yl)methanesulfonate scorpionate ligand, pz2CHSO3, relative to the monodentate ligands have been optimized. A two-step mechanism is proposed for the ligand substitution reaction that is consistent with the computational results and the weak coordination of the sulfonate group.  相似文献   

20.
《Inorganica chimica acta》2001,312(1-2):15-22
The synthesis, characterization and reactivity of trans-[NO(L)(NH3)4Ru]Cl3 (L=imidazole, theophylline and caffeine) are presented. 1H NMR spectroscopy indicates that the imidazole ligands are coordinated to the RuII through a carbon atom (imκ2, 1,3Me2Xanκ8 and 1,3,7Me3Xanκ8). The nitrosyl stretching frequencies (νNO≅1913 cm−1) suggest the coordinated nitrosyl has substantial NO+ character. The complexes undergo a single-electron reduction (E°≅−0.50 V versus Ag/AgCl), which involves the coordinated nitrosyl. Dissociation of NO· in the reduced species is facilitated by the trans-imidazolylidene ligand. The lower than expected reduction potentials of these complexes may account for their inactivity in evoking neuronal firing in the hippocampus by releasing NO following reduction.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号