Synthesis,characterisation and biological activity of cycloaurated organogold(III) complexes with imidate ligands

The reactions of the cycloaurated gold(III) complexes (2-bp)AuCl₂ (2-bp = 2-benzylpyridyl) or (damp)AuCl₂ (damp = Me₂NCH₂C₆H₄) with an excess of sodium saccharinate (Nasacc), potassium phthalimidate (Kphth), or with isatin and trimethylamine in refluxing methanol results in the successful isolation of a series of new gold(III) imidate complexes. These were characterised by NMR and IR spectroscopies, and by X-ray structure determinations on (2-bp)Au(sacc)₂ and (2-bp)Au(phth)₂. In both structures, the planes of the saccharinate and the phthalimidate ligands are orientated almost perpendicular to the gold coordination plane. As expected from trans-influence considerations, the Au–N_(imidate) bond lengths trans to the aryl carbon atoms are longer than the Au–N_(imidate) bond lengths trans to the pyridyl groups. The complexes have also been characterised by electrospray ionisation MS; in the presence of halide ligands, one imidate ligand is readily displaced. Anti-tumour (P388 murine leukemia) and selected anti-microbial data for the new complexes are reported. Surprisingly, all three damp complexes had low anti-tumour activity, which is likely to be a consequence of the poor solubility of these complexes. The synthesis and characterisation of a related gold(III) bis(amidate) complex derived from sulfathiazole is also described.     

Synthesis, characterisation and biological activity of gold(III) catecholate and related complexes

The reactions of the cyclometallated gold(III) complexes [LAuCl₂] [L=2-(dimethylaminomethyl)phenyl, 2-benzylpyridyl or 2-anilinopyridyl] with catechol, tetrachlorocatechol, or the cyclic α,β-diketone SCH(CO2Et)C(O)C(O)CH(CO2Et) give stable complexes containing five-membered Au-O-C-C-O rings. These represent the first examples of well-characterised gold(III) catecholate complexes. Similarly, reactions with 2-acetamidophenol [HOC₆H₄NHC(O)CH₃] give complexes with the related AuNCCO ring. The complexes were characterised by NMR spectroscopy, electrospray ionisation mass spectrometry, elemental microanalysis, and in the case of the complex [(2-benzylpyridyl)Au{OC₆H₄NC(O)CH₃}] by an X-ray crystal structure determination. Several complexes show high activity towards P388 murine leukemia cells.     

Synthesis and characterisation of dimeric eight-coordinate lanthanide(III) complexes of a macrocyclic tribenzylphosphinate ligand

The macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7-triyl(methylenebenzyl-phosphinic acid) H3L3, has been prepared and its complexes with Eu, Gd and Tb(III) studied by NMR, relaxometry, luminescence and single crystal X-ray crystallography. In solution and in the crystal, the complexes have eight-coordinate metal centres with bridging phosphinate groups linking the two twisted square antiprismatic coordination polyhedra. A single stereoisomer crystallises from solution with an RRR and SSS configuration at the P centres in each sub-unit. The relaxivity of [GdL3]2 is low (1.9 mM-1 s-1, 298 K, 20 MHz), consistent with the absence of any proximate water molecules. The terbium dimer possesses a relatively long excited state lifetime (2.47 ms, 298 K).     

Organogold(III) complexes containing chelating bis(amidate) ligands: Synthesis,characterisation and biological activity

Reactions of cycloaurated gold(III) dichloride complexes, with 1,2-C₆H₄(NHCOMe)₂ and silver(I) oxide, or with C₂H₄(NHSO₂Tol)₂ (Tol = p-tolyl) or 1,2-C₆H₄(NHSO₂Tol)₂ and trimethylamine, give a series of new auracyclic complexes containing the Au–NR–CH₂CH₂–NR (R = SO₂Tol) and Au–NR–C₆H₄–NR (R = COMe or SO₂Tol) five-membered ring systems. An X-ray structure determination on (2-bp)Au{N(COMe)C₆H₄N(COMe)} (2-bp = cycloaurated 2-benzylpyridine) shows the presence of puckered metallacyclic rings, with both acetyl substituents positioned below the Au(III) coordination plane. The complex (2-bp)Au{N(COMe)C₆H₄N(COMe)} undergoes ring cleavage in the presence of halide and water, to give the complex (2-bp)Au{N(COMe)C₆H₄NH(COMe)}Cl, which was characterised crystallographically, and shown to contain a monodentate amidate ligand. Biological activity studies of the new auracyclic complexes are also reported, against P388 murine leukaemia cells and a range of bacteria and fungi, with a number of complexes showing high activity.     

Synthesis,characterization and biological evaluation of Ru(III) mercaptopyrimidine Schiff base complexes

A new series of mercaptopyrimidine Ru(III) complexes were synthesized and characterized using various spectral techniques like single‐crystal X‐ray diffraction, Fourier transform infrared and NMR spectroscopies, thermogravimetric analysis and energy‐dispersive X‐ray analysis. The complexes were evaluated for their pharmacological activities like in vitro antimicrobial, anticancer, antituberculosis and antioxidant activities. The DNA binding of the complexes was investigated by absorption and emission spectral measurements which indicated that the complexes bind to DNA via intercalation, with molecular docking studies validating the results. DNA cleavage studies of the complexes were carried out.     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(III) complexes

Seven new μ-isophthalato dinuclear lanthanide(III) complexes, namely [Ln₂(IPHTA)(Me₂-phen)₄-(ClO₄)₂](ClO₄)₂ (Ln=La, Nd, Sm, Eu, Gd, Ho, Er), where Me₂-phen denotes 2,9-dimethyl-1,10-phenanthroline (Me₂-phen), IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [ Gd₂ (IPHTA) (Me₂-phen)₄ ( ClO₄ )₂ ] ((ClO₄ )₂ complex were measured in the temperature range of 4–300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = -2JS₁. J₂. giving the exchange parameter J = -0.19 cm^?1. This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(III)-Gd(III) im within the complex.     

Organogold(III) metallacyclic chemistry. Part 4. Synthesis, characterisation, and biological activity of gold(III)-thiosalicylate and -salicylate complexes

The silver(I) oxide mediated reactions of the gold(III) dichloride complex [{C₆H₃(CH₂

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uCl₂] 2a with thiosalicylic or salicylic acid gives the respective complexes [{C₆H₃(CH₂

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)-2}] 3a (X=S) or 6b (X=O), containing chelating thiosalicylate or salicylate dianion ligands. X-ray studies show that for the thiosalicylate system, the thiosalicylate sulfur atom is trans to the N,N-dimethylamino group, whereas in the structure of the salicylate complex, it is the carboxylate group that is trans to NMe₂. Both complexes show puckered metallacycles in the solid state. Electrospray mass spectrometry (ESMS) shows strong [M+H]⁺ and [2M+H]⁺ ions for both the gold-thiosalicylate and -salicylate complexes, and these ions possess a high stability towards cone voltage-induced fragmentation. ESMS was also used to identify a minor impurity, the bis(cyclo-aurated) cationic complex [A

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Me₂)-2-(OMe)-5}2]⁺ in the starting dihalide complex 2a and in the product 3a. This complex can be formed by reaction of Me₄N[AuCl₄] with 2 equivalents of the organomercury precursor [Hg{C₆H₃(CH₂NMe₂)-2-(OMe)-5}Cl]. The biological (antitumour, antimicrobial and antiviral) activities are also reported, and these reveal the complexes have moderate to high anti-tumour, antibacterial and antifungal activity.     

Synthesis and characterisation of bis-cyclen based dinuclear lanthanide complexes

The design and synthesis of several bis-macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) ligands and their corresponding lanthanum or europium complexes is described; these dinuclear lanthanide systems were made by connecting two macrocyclic cyclen moieties through a rigid, covalent, p-xylylenediamide bridge or a flexible aliphatic hexane bridge. These ligands were subsequently functionalised with six acetamide pendant arms (CONR1R2: R1 = R2 = H or CH3, or R1 = H, R2 = CH3). The corresponding lanthanide bis-complexes were then formed by reaction with La(III) and Eu(III) triflates, yielding overall cationic (+VI charged) complexes.     

Thermal analysis of lanthanide(III) and Y(III) complexes with 4-hydroxy-3-methoxybenzoic acid

Summary A procedure for the extrapolation of accelerated thermo-oxidative ageing tests to lower temperatures is proposed. The procedure involves a deconvolution of the global process into high- and low-temperature components where the extrapolation to low temperatures is carried out using the low-temperature component. The method was tested on stabilized and unstabilized polyisoprene rubber and was found to produce realistic estimations of the length of the induction period of oxidation so giving a more accurate estimation of the service life. However, to obtain the low-temperature values of the adjustable kinetic parameters, very low heating rates are required (0.04 K min^-1, 0.1 K min^-1) making the measurement process time consuming. Using this method, more realistic estimates of the durability of a material are obtained.     

Synthesis,characterisation, crystal structure and biological activity of metal(II) complexes with theophylline

Three metal complexes with empirical formulae [Mn(theop)₂(H₂O)₄] (1), [Co(theop)₂(H₂O)₄] (2), [Ni(theop)₂(H₂O)₄] (3), (where: theop?=?theophylline) were synthesized and characterized by elemental analysis, FTIR- spectroscopy and thermal decomposition techniques. Their crystal structures were determined by single crystal Xray diffraction analysis. Complexes are isomorphous and crystallise in the monocyclic space group P21/c. Their thermal behavior was studied by TGA methods under non-isothermal condition in air. Upon heating all compounds decompose progressively to metal oxides, which are the final products of pyrolysis. Furthermore, antimicrobial and antioxidant activity of the complexes was examined.     

Synthesis of stable monoporphyrinate lanthanide(III) complexes without ancillary ligands

A new type of porphyrin ligand bearing four triazole groups at the ortho-positions of phenyl rings in tetraphenylporphyrin was synthesized for the formation of monoporphyrinate lanthanide complexes without ancillary ligands.     

Synthesis and properties of lanthanide(III) complexes with 4-hydroxy-3,5-dimethoxybenzoic acid

Complexes of yttrium(III) and lanthanides(III) with 4-hydroxy-3,5-dimethoxybenzoic (syringic) acid were obtained as solids with metal to ligand mole ratio of 1: 3. The compounds were characterized by elemental analysis, IR spectroscopy, X-ray diffraction patterns, solubility, and thermal studies. The complexes are sparingly soluble in water and stable at room temperature. Compounds of light lanthanides (from La to Nd) are hydrated and they crystallize in a triclinic system. When heated, they lose water molecules in one step and in the next step they decompose to oxides. Complexes of yttrium and other lanthanides are anhydrous and crystallize in a monoclinic system. They are stable up to 300°C and then decompose to oxides. As the coordination number of lanthanide ions is usually equal to 9 or 8, one can suppose that hydroxy or methoxy groups take part in the coordination of these metal ions.     

Synthesis,structure, and catalytic activity of lanthanide Gd(III) and La(III) complexes with N-(cyclohexyl)isopropyl amidate ligand

Two new lanthanide amidate complexes, {Gd₂[Cy(NCO)ⁱPr]₆} (1) and {La₂[Cy(NCO)ⁱPr]₆[Cy(HNCO)ⁱPr]} (2) (ⁱPr = isopropyl, Cy = cyclohexyl), have been synthesized in good yields by silylamine elimination reaction between Gd[N(SiMe₃)₂]₃ or La[N(SiMe₃)₂]₃ and N-(cyclohexyl)isopropyl amide. Complexes 1 and 2 have been characterized by NMR, elemental analyzes, and X-ray diffraction. The molecular structures of {[Cy(NCO)ⁱPr]Gd[μ₂-Cy(NCO)ⁱPr]₃Gd[Cy(NCO)ⁱPr]₂} (1) and {[Cy(NCO)ⁱPr]La[μ₂-Cy(NCO)ⁱPr]₃La[Cy(NCO)ⁱPr]₂[Cy(HNCO)ⁱPr]} (2) exhibit a dimer structure with three μ₂-O bridging bonds that look like a windmill. Additionally, 2 formed an intramolecular N–H···O hydrogen bond via a neutral amide. The catalytic properties of 1 and 2 for ring-opening polymerization (ROP) of ε-caprolactone have been studied. The results show that 1 and 2 are efficient catalysts for the ROP of ε-caprolactone.     

Synthesis and characterisation of complexes of iron(II,III), cobalt(II,III) and nickel(II) with dinitrosoresorcinol

Summary Complexes of Fe^II, Fe^III, Co^II, Co^III and Ni^II with dinitroso resercinol (DNR) have been isolated and characterised. Ni studies showed that the metals are coordinated to the oxygens of one hydroxyl and one nitroso group, the second hydroxyl and nitroso groups remaining uncoordinated. The magnetic moments of the Fe^II and Ni^II complexes are commensurate with tetrahedral (or disorted octahedral) structures, while the others are ocahedral, however, the electronic spectra suggest ocahedral stereochemistries for all the complexes.     

Synthesis,spectral and pharmacological studies on lanthanide(III) complexes of 3,5-pyrazoledicarboxylic acid

Complexes of cerium(III), lanthanum(III) and neodymium(III) with 3,5-pyrazoledicarboxylic acid (H₃pdc) were synthesized and their compositions determined by elemental analysis. To identify the binding of Ce(III), La(III) and Nd(III) with H₃pdc, detailed vibrational analysis was performed comparing experimental vibrational spectra of the ligand and its Ln(III) complexes with theoretically predicted and with literature data from related compounds. Significant differences in the IR and Raman spectra of the complexes were observed as compared to spectra of the ligand. The ligand and the complexes were tested for cytotoxic activities on the chronic myeloid leukemia derived K-562, overexpressing the BCR-ABL fusion protein and the non-Hodgkin lymphoma derived DOHH-2, characterized by an overexpression of the antiapoptotic protein bcl-2 cell lines. The results indicate that the tested compounds exerted considerable cytotoxic activity upon the evaluated cell lines in a concentration dependent manner; we constructed dose-response curves and calculated corresponding IC₅₀ values. The lanthanide complexes exhibited potent cytotoxic activity, even more than cisplatin towards K-562 and DOHH-2 cell lines. In order to elucidate some of the mechanistic aspects of the observed cytotoxic effects, we evaluated whether the established cytotoxicity of the most active complex La(H₂pdc) is related to its capacity to induce cell death through apoptosis.     

X-ray studies of lanthanide(III) complexes with 4-hydroxy-3-methoxybenzoate anion

Polycrystalline complexes of lanthanide(III) with 4-hydroxy-3-methoxybenzoic acid were obtained as hydrated compounds of general formula Ln(C₈H₇O₄)₃?·?nH₂O. After slow recrystallization we obtained single crystals of complexes and determined their structures. Praseodymium(III) and neodymium(III) form isostructural dihydrated complexes [Ln(C₈H₇O₄)₃(H₂O)₂], which crystallize in the triclinic system, space group P 1. Sm(III), Eu(III), Gd(III), Ho(III) and Tb(III) compounds are hexahydrates and also crystallize in the triclinic system, space group P 1. Dihydrated compounds form polymeric chains with metal centres linked by oxygen atoms of bridging carboxylates. Each metal ion is coordinated by chelating carboxylic group and two water molecules. Complexes of the second isostructural group form dinuclear units [Ln₂(C₈H₇O₄)₆(H₂O)₄]?·?8H₂O. Lanthanide(III) ions are linked by oxygen atoms of two chelating–bridging carboxylate groups. In the dimeric structure each metal ion coordinates additionally two chelating carboxylic groups and two water molecules.     

Photo and electroluminescence of lanthanide(III) complexes

Major classes of coordination compounds used as electroluminescent materials are surveyed, and their advantages and disadvantages are discussed. The strategy of the directed synthesis of lanthanide(III) complexes promising for use as electroluminescent materials is formulated. The results of studies dealing with the design of electroluminescent devices based on europium(III), terbium(III), and thulium(III) complexes are considered.     

Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III)

The reactions of GaX3 (X = Cl, Br or I) with SMe2, SeMe2 and TeMe2 (L) in non-coordinating solvents produces only the pseudo-tetrahedral [GaX3L], which have been characterised by IR, Raman and multinuclear NMR (1H, 71Ga, 77Se or 125Te) spectroscopy, and by the crystal structure of [GaCl3(SeMe2)]. The 71Ga NMR resonances show small low frequency shifts for fixed halides as the neutral donors change from S --> Se --> Te. Bidentate ligands including MeS(CH2)2SMe, PhS(CH2)2SPh, MeSe(CH2)2SeMe, nBuSe(CH2)2Se(n)Bu and MeTe(CH2)3TeMe (L-L) also produce complexes with 4-coordinate gallium centres, [(GaX3)2(mu-L-L)], confirmed by the crystal structures of [(GaI3)2(mu-MeS(CH2)2SMe)], [(GaCl3)2(mu-PhS(CH2)2SPh)] and [(GaCl3)2(mu-nBuSe(CH2)2Se(n)Bu)]. The structural data are consistent with the weaker Lewis acidity of the gallium as the halide co-ligands become heavier. Multinuclear NMR studies suggest that in chlorocarbon solutions partial dissociation of the ligands occur, which increases with the halide co-ligand Cl < Br < I. The o-xylyl dithioether, o-C6H4(CH2SMe)2, despite being pre-organised for chelation, also forms [(GaCl3)2(mu-L-L)]. The corresponding diselenoether complex decomposes in solution with C-Se bond cleavage to form the selenonium salt [o-C6H4CH2Se(Me)CH2][GaCl4], which was structurally characterised. The ditelluroether o-C6H4(CH2TeMe)2 undergoes rapid C-Te bond fission and rearrangement upon reaction with GaCl3, and the telluronium species [o-C6H4CH2Te(Me)CH2]+ and [MeTe(CH2(o-C6H4)CH2TeMe)2]+ have been identified by ES+ mass spectrometry from their characteristic isotope patterns.     

Synthesis,characterization, and biological activity of some lanthanide ternary complexes

Five complexes have been synthesized by the reaction of lanthanide(III) nitrate with 2-thenoyltrifluoroacetone (HTTA) and p-hydroxybenzoic acid (L). The complexes have been characterized by elemental analysis, molar conductivity, FT-IR, UV-Vis, ¹H NMR, TG-DTA, XPS, and transmission electron microscope. The general formula of the complexes is Na[Ln(TTA)₃L] (Ln?=?La³⁺,?Ce³⁺,?Nd³⁺,?Eu³⁺,?Er³⁺). The antibacterial activities indicate that all five complexes exhibit antibacterial ability against Escherichia coli and Staphylococcus aureus with broad antimicrobial spectrums. The antitumor activity of the five complexes against K562 tumor cell in vitro is measured using methyl thiazolyl tetrazolium (MTT) colorimetry. The results show that the complexes induce K562 tumor cell apoptosis, and the complexes exhibit inhibitory effect on leukemia K562 cells.     

Synthesis,structural characterization and biological studies of neodymium(III) and samarium(III) complexes with mercaptotriazole Schiff bases

A series of neodymium(III) and samarium(III) complexes of type [Ln(L)Cl(H₂O)₃] have been synthesized with Schiff bases (LH₂) derived from 3‐(phenyl/substituted phenyl)‐4‐amino‐5‐mercapto‐1,2,4‐triazoles and isatin. The structures of the complexes were established using elemental analysis, molar conductivities, magnetic moments, infrared, NMR (¹H, ¹³C) and UV–visible spectra, X‐ray diffraction and mass spectrometry. The thermal behaviour of these compounds under non‐isothermal conditions was investigated using thermogravimetry and differential thermogravimetry. The intermediates obtained at the end of various thermal decomposition steps were identified from elemental analysis and infrared spectral studies. All the ligands and their complexes were also screened for their antibacterial activity against Staphylococcus aureus and Bacillus subtilis and antifungal activity against Aspergillus niger, Aspergillus flavus and Colletotrichum capsici. The screening results were correlated with the structural features of the compounds. Copyright © 2015 John Wiley & Sons, Ltd.