Ruthenium(II) chalconate complexes: Synthesis, characterization, catalytic, and biological studies

A series of new hexa-coordinated ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = 2′-hydroxychalcones) have been prepared by reacting [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with 2′-hydroxychalcones in benzene under reflux. The new complexes have been characterized by analytical and spectral (IR, electronic, ¹H, ³¹P and ¹³C NMR) data. Based on the above data, an octahedral structure has been assigned for all the complexes. The new complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant and also found efficient catalyst in the transfer hydrogenation of ketones. The antifungal properties of the complexes have also been examined and compared with standard Bavistin.     

Synthesis and spectral studies of [RuCl(CO)(L)(PPh3)(B)] (HL = 2'-hydroxychalcones and B = PPh3, pyridine or piperidine) and their catalytic and biological applications

The reactions of [RuHCl(CO)(PPh3)2(B)] (B = PPh3, pyridine or piperidine) and 2'-hydroxychalcones led to the formation of [RuCl(CO)(PPh3)(L)(B)] (L = chalconate). The new complexes have been characterized by analytical and spectral (IR, electronic, 1H NMR and 31P NMR) data. They have been assigned an octahedral structure. The complexes have been used as catalysts for the aerial oxidation of cinnamyl alcohol. Some of the complexes have been tested in vitro for growth inhibitory activity against the bacteria E. coli, S. typhi and Pseudomonas sp. and the fungi A. fumigatus.     

Synthesis,spectral, and catalytic studies of ruthenium(II) unsymmetrical Schiff-base complexes

Unsymmetrically-substituted ruthenium(II) Schiff-base complexes, [Ru(CO)(B)(L ^x )] [B = PPh₃, AsPh₃ or Py; L ^x = dianion of tetradentate unsymmetrical Schiff-base ligand; x = 4–7, L⁴ = salen-o-hyac, L⁵ = valen-o-hyac, L⁶ = salphen-o-hyac, L⁷ = valen-2-hacn], were prepared and characterized by analytical, IR, electronic, and ¹H NMR spectral studies. The new complexes were tested for their catalytic activity towards the oxidation of benzylalcohol to benzaldehyde.     

Synthesis,characterization and catalytic studies of ruthenium(II) chalconate complexes

Stable ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = 2′‐hydroxychalcones) were synthesized from the reaction of [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with 2′‐hydroxychalcones in benzene under reflux. The new complexes were characterized by analytical and spectroscopic (IR, electronic ¹H, ³¹P and ¹³C NMR) data. They were assigned an octahedral structure. The complexes exhibited catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N‐methylmorpholine‐N‐oxide (NMO) as co‐oxidant and were also found to be efficient transfer hydrogenation catalysts. Copyright © 2008 John Wiley & Sons, Ltd.     

Spectral,catalytic, and antifungal studies of ruthenium(II) chalcone complexes

Reactions of [RuHCl(CO)(B)(EPh₃)₂] (B = EPh₃ or Py; E = P or As) and chalcones in benzene with equal molar ratio led to the formation of new complexes of the type [RuCl(CO)(EPh₃)(B)(L^1?4)] (B = PPh₃, AsPh₃ or Py; E = P or As; L = chalcone). The new complexes have been characterized by analytical and spectroscopic (IR-, electronic, ¹H-, ³¹P-, and ¹³C-NMR) data. Based on these data, an octahedral structure has been assigned for all the complexes. The chalcones are monobasic bidentate (O,O) donors and coordinate to ruthenium via phenolic and carbonyl oxygen. The new complexes exhibit efficient catalytic activity for the transfer hydrogenation of carbonyl compounds. Antifungal properties of the ligands and their complexes have been examined and compared with standard Bavistin.     

Synthesis,spectral characterization,antioxidant, anticancer in vitro,and DNA cleavage studies of a series of ruthenium(II) complexes bearing Schiff base ligands

Ruthenium(II) complexes with 2-acetylpyridine-thiosemicarbazones (L¹–L⁴) were synthesized and characterized by analytical and spectral (FT-IR, UV–vis, NMR [¹H, ¹³C and ³¹P], and ESI-Mass) methods. Systematic biological investigations, free radical scavenging, anticancer activities, and DNA cleavage studies, were carried out for the complexes. Antioxidant studies showed that the complexes have significant antioxidant activity against DPPH, hydroxyl, nitric oxide radicals and hydrogen peroxide assay. The in vitro cytotoxicity of complexes against breast cancer (MCF-7) cell line was assayed showing high cytotoxicity with low IC₅₀ values indicating their efficiency in destroying the cancer cells even at very low concentrations. The DNA cleavage studies showed that the complexes efficiently cleaved DNA.     

Ruthenium(II) unsymmetrical N2O2 tetradentate Schiff-base complexes: synthesis,characterization, and catalytic studies

A series of six-coordinate ruthenium(II) complexes [Ru(CO)(L ^x )(B)] (B = PPh₃, AsPh₃ or Py; L ^x = unsymmetrical tetradentate Schiff base, x = 5–8; L⁵= salen-2-hyna, L⁶= Cl-salen-2-hyna, L⁷= valen-2-hyna, L⁸= o-hyac-2-hyna) have been prepared by reacting [RuHCl(CO)(EPh₃)₂(B)] (E = P or As) with unsymmetrical Schiff bases in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (infrared, electronic, ¹H, ³¹P, and ¹³C NMR) data. An octahedral structure has been assigned for all the complexes. The new complexes are efficient catalysts for the transfer hydrogenation of ketones and also exhibit catalytic activity for the carbon–carbon coupling reactions.     

Synthesis,characterization, and antitumor properties of ruthenium(II) anthraquinone complexes

Three new Ru(II) complexes, [Ru(dmb)₂(ipad)](ClO₄)₂ (dmb = 4,4′-dimethyl-2,2′-bipyridine, ipad = 2-(anthracene-9,10-dione-2-yl) imidazo[4,5-f][1,10]phenanthroline, 1), [Ru(dmp)₂(ipad)](ClO₄)₂ (dmp = 2,9-dimethyl-1,10-phenanthroline, 2), and [Ru(dip)₂(ipad)](ClO₄)₂ (dip = 4,7-diphenyl-1,10-phenanthroline, 3), have been synthesized and characterized. The three Ru(II) complexes intercalate with the base pairs of DNA. The in vitro antiproliferative activities and apoptosis-inducing characteristics of these complexes were investigated. The complexes exhibited cytotoxicity against various human cancer cell lines. BEL-7402 cells displayed the highest sensitivity to 1, accounted for by the greatest cellular uptake. Complex 1 was shown to accumulate preferentially in the nuclei of BEL-7402 cells and cause DNA damage and induce apoptosis, which involved cell cycle arrest and reactive oxygen species generation.     

Synthesis,spectral studies of copper(II)tetrathiocyanato dithallate(I) complexes with some acylhydrazones and their antimicrobial activity

Heterobimetallic complexes of Cu[Tl(SCN)₂]₂ ·; L (where L?=?acetophenone benzoylhydrazone(abh), acetophenone isonicotinoyl hydrazone(ainh), acetophenone salicyloylhydrazone(ash), acetophenone anthraniloyl hydrazone(aah), p-hydroxy acetophenone benzoylhydrazone (phabh), p-hydroxy acetophenone isonicotinoyl hydrazone (phainh), p-hydroxy acetophenone salicyloylhydrazone(phash) and p-hydroxy acetophenone anthraniloyl hydrazone(phaah) were synthesized and characterized. Electronic spectra and μ_eff values suggest a distorted octahedral environment around copper(II). SCN groups bridge between two metal centers and the ligands are coordinated through >C=O and >C=N–groups. Thermal studies (TGA and DTA) on Cu[Tl(SCN)₂]₂?·?ainh indicate multi step decomposition of both endothermic and exothermic nature. ESR data show axial spectra for all the complexes and d _{x²???y ²} as the ground state. Powder X-ray diffraction parameters for some of the complexes correspond to orthorhombic crystal lattice. The complexes show significant antifungal activity against Rizoctonia sp. and Stemphylium sp. and moderate antibacterial activity against Clostridium sp. and Pseudomonas sp. The activity increases at higher concentration of the compound.     

Synthesis and physico-chemical studies of metal(II) complexes with diacetyl benzaldehyde acyldihydrazones and their bio-activity

Complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with diacetyl benzaldehyde oxalic acid dihydrazone (dbodh), CH₃COC(CH₃)=NNHCOCONHN=CHC₆H₅ and diacetyl benzaldehyde malonic acid dihydrazone (dbmdh), CH₃COC(CH₃)=NNHCOCH₂CONHN=CHC₆H₅ of general composition [M(dbodh)Cl]Cl and [M(dbmdh)Cl]Cl were synthesized and characterized by microanalyses, molar conductance, magnetic susceptibility, UV–Vis, ESR and IR spectra and X-ray diffraction studies. The complexes are 1 : 1 electrolytes in DMF and are insoluble in water and common organic solvents. The dbodh and dbmdh are neutral tridentate ligands in most complexes and coordinate via one >C=O and two >C=N–groups. In Cu(II) complexes the ligands are pentadentate coordinating through three >C=O and two >C=N–groups. The magnetic moment values and UV–Vis spectra suggest square-planar geometry for Co(II) and Ni(II) complexes and distorted octahedron for both Cu(II) complexes. The ESR spectra of Cu(II) complexes show well-defined copper hyperfine lines in DMSO solution at 120 K and exhibit d _{x ² ?y ²} as the ground state. The X-ray diffraction parameters for [Ni(dbodh)Cl]Cl and [Co(dbmdh)Cl]Cl correspond to a tetragonal crystal lattice. The complexes show significant antifungal activity against Alternaria sp., Curvularia sp. and Colletotrichum sp. and fair antibacterial activity against Bacillus subtilis and Pseudomonas fluorescence.     

Synthesis,characterization and catalytic activity of halo-methyl-bis(salicylaldehyde)ethylenediamine cobalt(II) complexes

The synthesis, characterization and catalytic activity of a series of tetra-halo-dimethyl salen and di-halo-tetramethyl-salen ligands are reported in this paper: α,α′-dimethyl-Salen (dMeSalen) (L¹); 3,3′,5,5′-tetrachloro-α,α′-dimethyl-Salen, (tCldMeSalen) (L²); 3,3′-dibromo-5,5′-dichloro-α,α′-dimethyl-Salen, (dCldBrdMeSalen) (L³); 3,3′,5,5′-tetrabromo-α,α′-dimethyl-Salen, (tBrdMeSalen) (L⁴); 3,3′,5,5′-tetraiodo-α,α′-dimethyl-salen, (tIdMeSalen) (L⁵); 3,3′-dichloro-5,5′,α,α′-tetramethyl-Salen (dCltMeSalen) (L⁶); 3,3′-dibromo-5,5′,α,α′-tetramethyl-Salen (dBrtMeSalen) (L⁷); and 3,3′-diiodo-5,5′,α,α′-tetramethyl-Salen (dItMeSalen) (L⁸) (Salen = bis(salicylaldehyde)ethylenediamine). Upon reaction with Co(II) ions, these ligands form complexes with square planar geometry that have been characterized by elemental analysis, cyclic voltammetry, UV–Vis, IR and EPR spectroscopies. In the presence of pyridine the obtained Co(II) complexes were found able to bind reversibly O₂, which was shown by EPR spectroscopy and cyclic voltammetry. They were also found able to catalyze the oxidation of 2,6-di-tert-butylphenol (DtBuP) (9) with formation of 2,6-di-tert-butyl-1,4-benzoquinone (DtBuQ) (10) and 2,6,2′,6′-tetra-tert-butyl-1,1′-diphenobenzoquinone (TtBuDQ) (11). These properties are first influenced by the coordination of pyridine in axial position of the Co(II) ion that causes an increase of the electronic density on the cobalt ion and as a consequence a decrease in the E_1/2 value and an increase of the reducing power of the Co(II) complex. It is noteworthy that, under those conditions the complexes also show a remarkable quasi-reversible behaviour. Second, complex properties are also influenced by the substituents (methyl and halogen) grafted on the aromatic ring and on the azomethynic groups. The donating methyl substituent on the azomethynic groups causes a decrease in the E_1/2 value, whereas the halogen substituents on the aromatic rings have two effects: a mesomeric donating effect that tends to lower the redox potential of the complex, and a steric effect that tends to decrease the conjugation of the ligand and then to increase the redox potential of the Co(II) complex. In pyridine, the steric effect predominates, which causes both an increase of the redox potential and a decrease of the selectivity of the oxidation of phenol 9. As a result of all these effects, it then appears that the best catalysts to realize the selective oxidation of 2,6-di-tert-butyl-phenol (9) by O₂ are the Co complexes of ligands bearing CH₃ donating substituents, Co(dMeSalen) 1 (2CH₃ substituents), and Co-di-halo-tetra-methyl-salen complexes 6, 7 and 8 (4CH₃ substituents), in the presence of pyridine.     

Ruthenium(III) chalconate complexes containing PPh3/AsPh3 and their use as catalysts

Ruthenium(III) complexes of the type [RuX(EPh₃)(L)₂] (X?=?Cl or Br; E?=?P or As; L?=?2-hydroxychalcone) have been prepared by reacting [RuX₃(EPh₃)₃] with 2-hydroxychalcones in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (infrared, electronic, electron paramagnetic resonance, and mass) methods. Redox potential studies of the complexes have been carried out to elucidate the electronic structure, geometry, and electrochemical features. On the basis of data obtained, an octahedral structure has been assigned for all the complexes. The new complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide as co-oxidant and they were also found to be efficient catalyst for the transfer hydrogenation of ketones.     

Synthesis,crystal structure and catalytic activity of ruthenium(II) carbonyl complexes containing ONO and ONS donor ligands

Diamagnetic ruthenium(II) complexes of the type [Ru(L)(CO)(B)(EPh₃)] [where E = As, B = AsPh₃; E = P, B = PPh₃, py (or) pip and L = dibasic tridentate ligands dehydroacetic acid semicarbazone (abbreviated as dhasc) or dehydroacetic acid phenyl thiosemicarbazone (abbreviated as dhaptsc)] were synthesized from the reaction of [RuHCl(CO)(B)(EPh₃)₂] (where E = As, B = AsPh₃; E = P, B = PPh₃, py (or) pip) with different tridentate chelating ligands derived from dehydroacetic acid with semicarbazide or phenylthiosemicarbazide. All the complexes have been characterized by elemental analysis, FT-IR, UV–Vis and ¹H NMR spectral methods. The coordination mode of the ligands and the geometry of the complexes were confirmed by single crystal X-ray crystallography of one of the complexes [Ru(dhaptsc)(CO)(PPh₃)₂] (5). All the complexes are redox active and are monitored by cyclic voltammetric technique. Further, the catalytic efficiency of one of the ruthenium complexes (5) was determined in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide.     

Synthesis,spectroscopic characterization,and antimicrobial activities of Ni(II) and Fe(II) complexes with N-(2-hydroxyethyl)-5-nitrosalicylaldimine

Metal complexes [Ni(HL1)₂H₂O] (1) and [Fe(HL1)₂] (2), where HL1 is the tridentate Schiff base N-(2-hydroxyethyl)-5-nitrosalicylaldimine, were synthesized and characterized by spectroscopic methods. The crystal structures of 1 and 2 have been determined by single crystal diffraction at 100?K. Complexes 1 and 2 have a distorted octahedral geometry. The ligand and metal complexes were screened for antibacterial and antifungal activities by the disk diffusion, microdilution broth, and single spore culture techniques. Antimicrobial activities of the ligand and its complexes have been tested against 10 bacteria, two yeast, and five filamentous fungi. The ligand and metal complexes were found to be active against all tested micro-organisms.     

Synthesis,characterization and biological applications of new copper(II) complexes of aryl hydrazones

On treatment of copper(II) acetate with aryl hydrazone ligands, four new solid derivatives of copper(II) were produced in appreciable yields. Various characterization techniques including infrared, UV–visible, NMR, electron paramagnetic resonance and mass spectroscopies, elemental analysis, scanning electron microscopy, powder X‐ray diffraction and thermogravimetric analysis revealed a tetra‐coordination in all the mononuclear crystalline complexes with high thermal stability. Further, significant interaction of these novel complexes with calf thymus DNA via intercalative mode of binding was revealed by electronic absorption spectroscopy. The chemical nuclease activity of the complexes on pBR322 DNA was investigated in the presence and absence of oxidizing agent (H₂O₂). A potent nuclease activity was observed only in the presence of H₂O₂. Further, antibacterial and antifungal studies of the new ligands and complexes revealed that the latter possessed comparatively better activity.     

Syntheses,characterizations, and antimicrobial activities of binuclear ruthenium(III) complexes containing 2-substituted benzimidazole derivatives

Binuclear ruthenium(III) complexes [RuX₃L]₂?·?nH₂O (X?=?Cl, L?=?L¹, L², L³; n?=?1, L⁴ and L⁵, X?=?Br; L?=?L³), [RuX₃L_1.5]₂?·?nH₂O (X?=?Br, L?=?L¹; n?=?0, L⁴; n?=?6 and L⁵; n?=?10), and [RuX₃L₂]₂ (X?=?Br, L?=?L²) have been isolated by treatment of hydrated RuX₃ (X?=?Cl/Br) in acetone with 2-(2′-aminophenylbenzimidazole) (L¹), 2-(3′-aminophenylbenzimidazole) (L²), 2-[(3′-N-salicylidinephenyl)benzimidazole] (L³), 2-(3′-pyridylbenzimidazole) (L⁴), and 2-(4′-pyridylbenzimidazole) (L⁵) in acetone. The complexes were characterized by elemental analysis, conductivity and magnetic susceptibility measurements, IR, electronic, EPR, and mass spectral studies. The complexes were dimeric; based on analytical and spectral studies, an octahedral geometry was proposed for the complexes. The synthesized complexes were screened against Gram-positive and Gram-negative bacteria and fungi.     

Synthesis,spectral characterization,anticancer and antibacterial studies of cyclodiphosph(V)azane derivatives and their copper(II) complexes

The new cyclodiphosph(V)azane derivatives (1,3-dimethyl-2,4-dioxo-2',4'-bis(2,4-bis(dimethylaminopropylimino)cyclodiphosph(V)azane (H₂L¹) (1,3-dimethyl-2,4-dioxo-2',4'-bis(2,4-bis(dimethylaminoethylimino)cyclodiphosph(V)azane (H₂L²) and (1,3-dimethyl-2,4-dioxo-2'-(dimethylaminoethylimino)-4'-(dimethylaminopropyl-imino)cyclodiphosph(V)azane (H₂L³) containing four active coordination centers (NNNN) and their Cu(II) complexes have been synthesized and characterized by elemental analyses, spectroscopic methods, molar conductance as well as thermal and magnetic measurements. The UV–Vis and mass spectra of the ligands and their Cu(II) complexes were also recorded. The copper(II) complexes were found to have magnetic moments of 1.58–1.69 B. M. corresponding to one unpaired electron. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies. The absence of water molecules in all complexes was supported by thermal studies. All the thermal decomposition processes ended with the formation of CuO. The kinetic and thermodynamic parameters have been calculated. The ligand (H₂L³) and its Cu(II) complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and minimum inhibitory concentration was calculated. The screening was extended to the antibacterial activity using Kirby–Bauer single disk susceptibility test for all compounds.     

Synthesis,characterization, and catalytic properties of some new ruthenium(II)/(III) complexes containing N,N-donor ligands

This article describes the preparation and characterization of cis-[Ru(bipy)₂L](ClO₄)₂ and trans-[RuCl₂L₂]?·?Cl (bipy?=?2,2′-bipyridyl and L?=?ortho-phenylenediamine (o-phd), 2-aminopyridine (2-apy) and 2-aminobenzonitrile (2-abn), and examines the catalytic oxidations of benzyl alcohol, benzohydrol and pipronyl alcohol by cis-[Ru(bipy)₂ (o-phd)](ClO₄)₂ and trans-[RuCl₂(o-phd)₂]?·?Cl complexes at room temperature and in the presence of N-methyl morpholine-N-oxide (NMO) as co-oxidant.     

New mixed ligand complexes of ruthenium(II) that incorporate a modified phenanthroline ligand: Synthesis, spectral characterization and DNA binding

The hexafluorophosphate and chloride salts of two ruthenium(II) complexes, viz. [Ru(phen)(ptzo)₂]² and [Ru(ptzo)₃]²⁺, where ptzo = 1,10-phenanthrolino[5,6-e]1,2,4-triazine-3-one (ptzo) — a new modified phenanthroline (phen) ligand, have been synthesised. These complexes have been characterised by infrared, UV-Vis, steady-state emission and¹H NMR spectroscopic methods. Results of absorption and fluorescence titration as well as thermal denaturation studies reveal that both thebis- and tris-complexes of ptzo show moderately strong affinity for binding with calf thymus (CT) DNA with the binding constants being close to 10⁵M^-1 in each case. An intercalative mode of DNA binding has been suggested for both the complexes. Emission studies carried out in non-aqueous solvents and in aqueous media without DNA reveal that both [Ru(phen)(ptzo)₂]²⁺ and [Ru(ptzo)₃]²⁺ are weakly luminescent under these solution conditions. Successive addition of CT DNA to buffered aqueous solutions containing [Ru(phen)(ptzo)₂]²⁺results in an enhancement of the emission. These results have been discussed in the light of the dependence of the structure-specific deactivation processes of the MLCT state of the metallo-intercalator with the characteristic features of its DNA interaction. In doing so, attempts have been made to compare and contrast its properties with those of the analogous phenanthroline-based complexes including the ones reported by us previously.