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1.
Hereby we present the synthesis of several ruthenium(II) and ruthenium(III) dithiocarbamato complexes. Proceeding from the Na[trans‐RuIII(dmso)2Cl4] ( 2 ) and cis‐[RuII(dmso)4Cl2] ( 3 ) precursors, the diamagnetic, mixed‐ligand [RuIIL2(dmso)2] complexes 4 and 5 , the paramagnetic, neutral [RuIIIL3] monomers 6 and 7 , the antiferromagnetically coupled ionic α‐[RuIII2L5]Cl complexes 8 and 9 as well as the β‐[RuIII2L5]Cl dinuclear species 10 and 11 (L=dimethyl‐ (DMDT) and pyrrolidinedithiocarbamate (PDT)) were obtained. All the compounds were fully characterised by elemental analysis as well as 1H NMR and FTIR spectroscopy. Moreover, for the first time the crystal structures of the dinuclear β‐[RuIII2(dmdt)5]BF4 ? CHCl3 ? CH3CN and of the novel [RuIIL2(dmso)2] complexes were also determined and discussed. For both the mono‐ and dinuclear RuII and RuIII complexes the central metal atoms assume a distorted octahedral geometry. Furthermore, in vitro cytotoxicity of the complexes has been evaluated on non‐small‐cell lung cancer (NSCLC) NCI‐H1975 cells. All the mono‐ and dinuclear RuIII dithiocarbamato compounds (i.e., complexes 6 – 10 ) show interesting cytotoxic activity, up to one order of magnitude higher with respect to cisplatin. Otherwise, no significant antiproliferative effect for either the precursors 2 and 3 or the RuII complexes 4 and 5 has been observed.  相似文献   

2.
The tri­chloro‐bridged dinuclear RuII complex tri‐μ‐chloro‐bis{[1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane‐κ3P,P′,P′′]ruthenium(II)} hexa­fluoro­phosphate ethanol solvate, [Ru2Cl3(tripod)2]PF6·C2H6O, containing the tripod [1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane, C41H39P3] ligand, was unexpectedly obtained from the reaction of [RuIIICl3(tripod)] with 1,4‐bis­(di­phenyl­phosphino)­butane (dppb), followed by pre­cipitation with NH4PF6. The magnetic moment of the compound at room temperature indicates that the dinuclear [Ru2(μ‐Cl)3(tripod)2]+ cation is diamagnetic. A single‐crystal X‐ray structure determination revealed that the two Ru atoms are bridged by the three Cl atoms. The coordination sphere of each Ru atom is completed by the three P atoms of a tripod ligand. The two P3Ru units are exactly eclipsed, while the bridging Cl atoms are staggered with respect to the six P atoms. The Ru⋯Ru distance is 3.3997 (7) Å and the mean Cl—Ru—Cl bond angle is 77.7°.  相似文献   

3.
The title compound, catena‐poly[[tetrakis(μ‐decanoato‐κ2O:O′)diruthenium(II,III)(RuRu)]‐μ‐octanesulfonato‐κ2O:O′], [Ru2(C10H19O2)4(C8H17O3S)], is an octane­sulfonate derivative of the mixed‐valence complex diruthenium tetradecanoate. The equatorial carboxyl­ate ligands are bidentate, bridging two Ru atoms to form a dinuclear structure. Each of the two independent dinuclear metal complexes in the asymmetric unit is located at an inversion centre. The octane­sulfonate anion bridges the two dinuclear units through axial coordination. The alkyl chains of the carboxyl­ate and sulfonate ligands are arranged in a parallel manner. The global structure can be seen as infinite chains of polar moieties separated by a double layer of non‐polar alkyl groups, without interdigitation of the alkyl chains.  相似文献   

4.
The complex cis‐[RuIII(dmbpy)2Cl2](PF6) ( 2 ) (dmbpy = 4, 4′‐dimethyl‐2, 2′‐bipyridine) was obtained from the reaction of cis‐[RuII(dmbpy)2Cl2] ( 1 ) with ammonium cerium(IV) nitrate followed by precipitation with saturated ammonium hexafluoridophosphate. The 1H NMR spectrum of the RuIII complex confirms the presence of paramagnetic metal atoms, whereas that of the RuII complex displays diamagnetism. The 31P NMR spectrum of the RuIII complex shows one signal for the phosphorus atom of the PF6 ion. The perspective view of each [RuII/III(dmbpy)2Cl2]0/+ unit manifests that the ruthenium atom is in hexacoordinate arrangement with two dmbpy ligands and two chlorido ligands in cis position. As the oxidation state of the central ruthenium metal atom becomes higher, the average Ru–Cl bond length decreases whereas the Ru–N (dmbpy) bond length increases. The cis‐positioned dichloro angle in RuIII is 1.3° wider than that in the RuII. The dihedral angles between pair of planar six‐membered pyridyl ring in the dmbpy ligand for the RuII are 4.7(5)° and 5.7(4)°. The observed inter‐planar angle between two dmbpy ligands in the RuII is 89.08(15)°, whereas the value for the RuIII is 85.46(20)°.  相似文献   

5.
Using a new mononuclear “building block,” for the first time, a dinuclear RuII(dppn) complex and a heteroleptic system containing both RuII(dppz) and RuII(dppn) moieties are reported. The complexes, including the mixed dppz/dppn system, are 1O2 sensitizers. However, unlike the homoleptic dppn systems, the mixed dppz/dppn complex also displays a luminescence “switch on” DNA light‐switch effect. In both cisplatin sensitive and resistant human ovarian carcinoma lines the dinuclear complexes show enhanced uptake compared to their mononuclear analogue. Thanks to a favorable combination of singlet oxygen generation and cellular uptake properties all three of the new complexes are phototoxic and display potent activity against chemotherapeutically resistant cells.  相似文献   

6.
Using a new mononuclear “building block,” for the first time, a dinuclear RuII(dppn) complex and a heteroleptic system containing both RuII(dppz) and RuII(dppn) moieties are reported. The complexes, including the mixed dppz/dppn system, are 1O2 sensitizers. However, unlike the homoleptic dppn systems, the mixed dppz/dppn complex also displays a luminescence “switch on” DNA light‐switch effect. In both cisplatin sensitive and resistant human ovarian carcinoma lines the dinuclear complexes show enhanced uptake compared to their mononuclear analogue. Thanks to a favorable combination of singlet oxygen generation and cellular uptake properties all three of the new complexes are phototoxic and display potent activity against chemotherapeutically resistant cells.  相似文献   

7.
The title compound, [Cu2(C16H24N2O)2Cl4], is a dinuclear copper(II) complex with inversion symmetry. Each CuII atom is five‐coordinated by two O and one N atom from two Schiff base ligands, and by two Cl atoms, giving an approximately trigonal–bipyramidal coordination environment.  相似文献   

8.
The complete sequence of reactions in the base‐promoted reduction of [{RuII(CO)3Cl2}2] to [RuI2(CO)4]2+ has been unraveled. Several μ‐OH, μ:κ2‐CO2H‐bridged diruthenium(II) complexes have been synthesized; they are the direct results of the nucleophilic activation of metal‐coordinated carbonyls by hydroxides. The isolated compounds are [Ru2(CO)4(μ:κ2C,O‐CO2H)2(μ‐OH)(NPF‐Am)2][PF6] ( 1 ; NPF‐Am=2‐amino‐5,7‐trifluoromethyl‐1,8‐naphthyridine) and [Ru2(CO)4(μ:κ2C,O‐CO2H)(μ‐OH)(NP‐Me2)2][BF4]2 ( 2 ), secured by the applications of naphthyridine derivatives. In the absence of any capping ligand, a tetranuclear complex [Ru4(CO)8(H2O)23‐OH)2(μ:κ2C,O‐CO2H)4][CF3SO3]2 ( 3 ) is isolated. The bridging hydroxido ligand in 1 is readily replaced by a π‐donor chlorido ligand, which results in [Ru2(CO)4(μ:κ2C,O‐CO2H)2(μ‐Cl)(NP‐PhOMe)2][BF4] ( 4 ). The production of [Ru2(CO)4]2+ has been attributed to the thermally induced decarboxylation of a bis(hydroxycarbonyl)–diruthenium(II) complex to a dihydrido–diruthenium(II) species, followed by dinuclear reductive elimination of molecular hydrogen with the concomitant formation of the RuI? RuI single bond. This work was originally instituted to find a reliable synthetic protocol for the [Ru2(CO)4(CH3CN)6]2+ precursor. It is herein prescribed that at least four equivalents of base, complete removal of chlorido ligands by TlI salts, and heating at reflux in acetonitrile for a period of four hours are the conditions for the optimal conversion. Premature quenching of the reaction resulted in the isolation of a trinuclear RuI2RuII complex [{Ru(NP‐Am)2(CO)}{Ru2(NP‐Am)2(CO)2(μ‐CO)2}(μ33C,O,O′‐CO2)][BF4]2 ( 6 ). These unprecedented diruthenium compounds are the dinuclear congeners of the water–gas shift (WGS) intermediates. The possibility of a dinuclear pathway eliminates the inherent contradiction of pH demands in the WGS catalytic cycle in an alkaline medium. A cooperative binuclear elimination could be a viable route for hydrogen production in WGS chemistry.  相似文献   

9.
We report the synthesis of a mixed‐valence ruthenium complex, bearing pyrene moieties on one side of the ligands as anchor groups. Composites consisting of mixed‐valence ruthenium complexes and SWNTs were prepared by noncovalent π–π interactions between the SWNT surface and the pyrene anchors of the Ru complex. In these composites, the long axis of the Ru complexes was aligned in parallel to the principal direction of the SWNT. The optimized conformation of these complexes on the SWNT surface was calculated by molecular mechanics. The composites were examined by UV/Vis absorption and FT‐IR spectroscopy, XPS, and SEM analysis. Furthermore, their electrochemical properties were evaluated. Cyclic voltammograms of the composites showed reversible oxidation waves at peak oxidation potentials (Epox) = 0.86 and 1.08 V versus Fc+/Fc, which were assigned to the RuII‐RuII/RuII‐RuIII and the RuII‐RuIII/RuIII‐RuIII oxidation events of the dinuclear ruthenium complex, respectively. Based on these observations, we concluded that the electrochemical properties and mixed‐valence state of the dinuclear ruthenium complexes were preserved upon attachment to the SWNT surface.  相似文献   

10.
The title compound, [Cu2(C13H14N3)2Cl2], is a neutral dimeric copper(II) complex. The two CuII atoms are asymmetrically bridged by two chloride ions. Each CuII atom is also bound to the three N atoms of a deprotonated tridentate Schiff base ligand, giving a distorted square‐pyramidal N3Cl2 coordination environment overall. The dinuclear complex lies across an inversion centre in the space group P. This work demonstrates the effect of ligand flexibility and steric constraints on the structures of copper(II) complexes.  相似文献   

11.
Metal complexes with Schiff base ligands have been suggested as potential phosphors in electroluminescent devices. In the title complex, tetrakis[6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolato‐1:2κ8N,N′,O:O;3:2κ8N,N′,O:O]trizinc(II) hexafluoridophosphate methanol monosolvate, [Zn3(C14H13N2O)4](PF6)2·CH3OH, the ZnII cations adopt both six‐ and four‐coordinate geometries involving the N and O atoms of tetradentate 6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolate ligands. Two terminal ZnII cations adopt distorted octahedral geometries and the central ZnII cation adopts a distorted tetrahedral geometry. The O atoms of the phenolate ligands bridge three ZnII cations, forming a dicationic trinuclear metal cluster. The title complex exhibits a strong emission at 469 nm with a quantum yield of 15.5%.  相似文献   

12.
The asymmetric unit of the title compound, [Pb2(C8H4O4)2(C18H11N5)2]n, contains two PbII atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each PbII atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc1 and 1,4‐bdc2) show different coordination modes. Each 1,4‐bdc1 coordinates to two PbII atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc2 anion connects two PbII atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.  相似文献   

13.
The title compound, trans‐[RuIICl2(N1‐mepym)4] (mepym is 4‐methylpyrimidine, C5H6N2), obtained from the reaction of trans,cis,cis‐[RuIICl2(N1‐mepym)2(SbPh3)2] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N1 and arranged in a propeller‐like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N3 and Cl atoms are involved in intermolecular C—H?N and C—­H?Cl hydrogen‐bond interactions.  相似文献   

14.
The title complex, di‐μ‐chloro‐bis­[chloro­(η6p‐cymene)ruthenium(II)]–9H‐carbazole (1/2), [Ru2Cl4(C10H14)2]·2C12H9N, is composed of one [RuCl26p‐cymene)]2 and two 9H‐carbazole mol­ecules. There are one‐half of a dinuclear complex and one 9H‐carbazole mol­ecule per asymmetric unit. In the dinuclear complex, each of the two crystallographically equivalent Ru atoms is in a pseudo‐tetra­hedral environment, coordinated by a terminal Cl atom, two bridging Cl atoms and the aromatic hydro­carbon, which is linked in a η6 manner; the Ru⋯Ru separation is 3.688 (3) Å. The title complex has a crystallographic centre of symmetry located at the mid‐point of the Ru⋯Ru line. Inter­molecular N—H⋯Cl and π–π stacking inter­actions are observed. These inter­actions form a four‐pointed star‐shaped ring and one‐dimensional linear chains of edge‐fused rings running parallel to the [100] direction, which stabilize the crystal packing.  相似文献   

15.
In the title complex, {[Cu(C6H5O3)Cl(H2O)]·H2O}n, the CuII atom has a deformed square‐pyramidal coordination geometry formed by two O atoms of the maltolate ligand, two bridging Cl atoms and the coordinated water O atom. The Cu atoms are bridged by Cl atoms to form a polymeric chain. The deprotonated hydroxyl and ketone O atoms of the maltolate ligand form a five‐membered chelate ring with the Cu atom. Stacking interactions and hydrogen bonds exist in the crystal.  相似文献   

16.
The EPR technique has been used to study the photolysis of the mixed-ligand complex CuII(Et2dtc)Br in a 1:1 solvent mixture of chloroalkane and alcohol, where the chloroalkane is CCl4, CHCl3 or CH2Cl2 and the alcohol is MeOH, EtOH, i-PrOH or i-BuOH, in comparison with CuII(Et2dtc)Cl photolysis in CHBr3:ROH. It was found that while CuII(Et2dtc)Br photolysis in chloroalkane:ROH yielded CuII(Et2dtc)Cl as an intermediate, the opposite conversion of CuII(Et2dtc)Cl to CuII(Et2dtc)Br proceeded via CuII(Et2dtc)Cl photolysis in CHBr3:ROH. The final photolytic products in both cases were tetraethylthiuramdisulphide and the corresponding copper(II) salt (CuCl2 or CuBr2, respectively). The results obtained by EPR allowed to get some insight into the behaviour of the primary photolytic products towards both components of the mixed solvent.  相似文献   

17.
The title compound, cis‐di‐μ‐perfluoroheptanoato‐κ4O:O′‐bis[dicarbonyl(dimethyl sulfoxide‐κS)ruthenium(I)](RuRu), [Ru2(C7F13O2)2(C2H6OS)2(CO)4], is a sawhorse‐type dinuclear ruthenium complex with two bridging perfluoroheptanoate ligands, and with two dimethyl sulfoxide (DMSO) ligands in the axial positions coordinating via the S atoms. It is a new example of a compound with an aliphatic fluorinated carboxylate ligand. The Ru—Ru bond distance of 2.6908 (3) Å indicates a direct Ru—Ru interaction. The compound is an active catalyst in transvinylation of propionic acid with vinyl acetate.  相似文献   

18.
In the title compound, [Mn(C5H2N2O4)(H2O)2]n, the MnII ion has a distorted octahedral geometry and the 4‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (Hiso2−) anion acts as a μ34‐bridging ligand. Two oxo O atoms from different Hiso2− ligands bridge two MnII ions, forming centrosymmetric dinuclear building blocks. Each dinuclear building block interacts with another four by the coordination of the oxide groups and carboxylate O atoms, producing a two‐dimensional framework in the ab plane. Hydrogen bonds further extend the two‐dimensional sheets into a three‐dimensional supramolecular framework.  相似文献   

19.
Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca2en, systematic name: (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ‐chlorido‐μ‐hydroxido‐bis(chlorido{(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ2N,N′}copper(II)) dichloromethane sesquisolvate, [Cu2Cl3(OH)(C20H18N4O4)2]·1.5CH2Cl2. The dinuclear complex has a folded four‐membered ring in an unsymmetrical Cu2OCl3 core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two CuII atoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca2en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five‐coordinate complex, of the Nca2en Schiff base ligand. Molecules of the dimer are associated in pairs by ring‐stacking interactions supported by C—H…Cl interactions with solvent molecules; a further ring‐stacking interaction exists between the two Schiff base ligands of each molecule.  相似文献   

20.
Schiff bases are considered `versatile ligands' in coordination chemistry. The design of polynuclear complexes has become of interest due to their facile preparations and varied synthetic, structural and magnetic properties. The reaction of the `ligand complex' [CuL] {H2L is 2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenol} with Ni(OAc)2·4H2O (OAc is acetate) in the presence of dicyanamide (dca) leads to the formation of bis(dicyanamido‐1κN1)bis(dimethyl sulfoxide)‐2κO,3κO‐bis{μ‐2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenolato}‐1:2κ6O,O′:O,N,N′,O′;1:3κ6O,O′:O,N,N′,O′‐dicopper(II)nickel(II), [Cu2Ni(C17H16N2O2)2(C2N3)2(C2H6OS)2]. The complex shows strong absorption bands in the frequency region 2155–2269 cm−1, which clearly proves the presence of terminal bonding dca groups. A single‐crystal X‐ray study revealed that two [CuL] units coordinate to an NiII atom through the phenolate O atoms, with double phenolate bridges between CuII and NiII atoms. Two terminal dca groups complete the distorted octahedral geometry around the central NiII atom. According to differential thermal analysis–thermogravimetric analysis (DTA–TGA), the title complex is stable up to 423 K and thermal decomposition starts with the release of two coordinated dimethyl sulfoxide molecules. Free H2L exhibits photoluminescence properties originating from intraligand (π–π*) transitions and fluorescence quenching is observed on complexation of H2L with CuII.  相似文献   

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