Synthesis and structure of palladium(II) mixed complexes with DNA purine or pyrimidine bases and imidazole derivatives. Part I

Summary Palladium(II) mixed ligand complexes with purine or pyrimidine and imidazole derivatives were prepared and characterized by i.r., Raman and electronic spectroscopy. The compounds have the general formula [Pd(L₁)(L₂)(X₂)]; where L₁ = adenine, guanine, hypoxanthine, cytosine, 2-aminopyrimidine, 4(6)-hydroxypyrimidine; L₂ = N-methylimidazole, N-ethylimidazole or N-propylimidazole; X = Cl or Br. The complexes are square planar with cis-halogens. The purine, pyrimidine and imidazole bases act as monodentate ligands coordinated via the N(7) of purine and N(3) of pyrimidine and imidazole.     

Synthesis and structures of platinum(II) mixed ligand complexes with purine or piyrimidine bases of DNA and imidazole derivatives. Part 2

Summary Platinum(II) mixed ligand complexes with either purine or pyrimidine and imidazole derivatives were prepared and characterized by i.r., Raman and electronic spectroscopy. The compounds had the general formula [PtL¹L²Cl₂], where L¹ = adenine, guanine, hypoxanthine, cytosine, 2-aminopyrimidine; L² =N-methylimidazole,N-ethyl-imidazole orN-propylimidazole. The platinum(II) complexes had a square planar structure withcis-halogens. Purine or pyrimidine and imidazole derivatived bases acted as monodentate ligands coordinated via the N(7) of purine and N(3) of pyrimidine and imidazole derivatives.     

Stable gold(III) complexes with thiosemicarbazone derivatives

Novel thiosemicarbazonato complexes of gold(III) have been prepared from reactions of [Au(damp-C1,N)Cl2(damp- = 2-(N,N-dimethylaminomethyl)phenyl) or [NBu4][AuCl4] with 2-pyridineformamide thiosemicarbazones (HL). The thiosemicarbazones deprotonate and coordinate as mononegative, tridentate NNS ligands to gold to give [Au(Hdamp-C1)(L)]Cl2 or [AuCl(L)]Cl complexes. The organometallic damp- ligand is protonated during the reactions and the Au-N bond is cleaved. The [AuCl(L)]+ cations represent the first gold(III) complexes with thiourea derivatives which are not stabilised by an additional organometallic ligand. Reactions of [NBu4][AuX4](X = Cl, Br) with diphenylthiocarbazone (dithizone) result in reduction of the metal and the formation of gold(I) complexes of the composition [AuX(SCN4-3,4-Ph2)] where SCN4-3,4-Ph2 is 3,4-diphenyltetrazole thione which is formed from cyclisation of dithizone.     

From diphosphane to diphosphodiide gold(III) derivatives of 1,2-diphosphinobenzene

Treatment of 1,2-diphosphinobenzene with [Au(C6F5)3(tht)] leads to the diphosphane derivative [{Au(C6F5)3}(1,2-PH2C6H4PH2)] (1), which further reacts with other pentafluorophenylgold(III) reagents in the presence of acetylacetonate as deprotonating agent to afford phosphane-phosphide complexes. The noncyclic PPN[{Au(C6F5)3}2(1,2-PHC6H4PH2)] (2; PPN = bis(triphenylphosphine)iminium) has been shown to be a useful starting material for the synthesis of higher nuclearity cyclic or noncyclic diphosphide or even diphosphodiide derivatives through similar reactions. The crystal structures of the trinuclear anionic NBu4[{Au(C6F5)3}(1,2-PHC6H4PH){Au(C6F5)2Cl}{mu-Au(C6F5)2}] (3) and the hexanuclear [{Au(C6F5)3}(1,2-PC6H4P){Au(C6F5)3}{mu-M(dppe)M}2] (M = Au (12), Ag (13)) have been established by X-ray diffraction methods, the last complexes having a bicyclic ring containing three intramolecular interactions between the M(I) centres.     

Self-catalytic mechanism of prebiotic reactions: From formamide to purine bases

Complete reaction pathway of prebiotic reactions for formation of the purine nucleobases adenine, hypoxanthine, guanine, isoguanine, 2,6-diaminopurine, and xanthine from pure formamide are presented. All reactants (hydrogen cyanide, ammonia, water, formic acid, urea) and catalysts (formamide and formimidic acid) needed in the self-catalyzed reactions are available from a starting compound, formamide. The required raw materials are obtained by partial decomposition of formamide.     

Isothermal titration calorimetry studies on the binding of DNA bases and PNA base monomers to gold nanoparticles

An isothermal titration calorimetric (ITC) investigation of the interaction of DNA bases and PNA base monomers with gold nanoparticles is described revealing a binding sequence in the order C > G > A > T. Direct measurement of the strength of interaction of ligands with nanogold by ITC has important implications in surface modification strategies for biomedical, catalysis, and nanoarchitecture applications.     

Thermal desorption behavior and binding properties of DNA bases and nucleosides on gold

A comparison of the binding of DNA bases (adenine, cytosine, guanine, and thymine) and nucleosides (2'deoxyadenosine, 2'deoxycytidine, 2'deoxyguanosine, and thymidine) to gold thin films is presented. Desorption of monolayer/submonolayer and multilayer films of the adsorbates on gold studied via temperature-programmed desorption (TPD) and reflection-absorption infrared (RAIR) spectroscopy reveals that there are major differences in the binding affinities of the different bases to gold, for example, thymine DeltaHdes = 111 +/- 2 kJ/mol compared to guanine DeltaHdes = 146 +/- 2 kJ/mol. The differences can be rationalized by molecular structures of the bases and their binding modes to gold surfaces deduced from IR data. Similar trends in desorption energies, shifted to lower desorption energy by more than 10 kJ/mol, are observed for deoxynucleoside layers on gold thin films.     

Gold(III) complexes with imidazole,benzoxazole, purine and pyrimidine derivatives

Summary The synthesis and characterization of Au^III complexes with several heterocyclic ligands are reported. The compounds have general formula [AuX₃(L)], where L =N-methylimidazole (N-MeIz),N-ethylimidazole (N-EtIz),N-propylimidazole (N-PrIz), benzoxazole (BO), 2-methylbenzoxazole (2-MeBO), 2,5-dimethylbenzoxazole (2,5-diMeBO), 2-amino-pyrimidine (2-APm), 4(6) -hydroxy-pyrimidine [4(6)-hydrPm] or hypoxanthine (Hypox) and X = Cl or Br. Elemental analysis, conductivity measurements and spectral studies were used for the characterization of the complexes. A square-planar geometry withN-bonded heterocyclic ligands is suggested.     

Complex formation between gadolinium(III) porphyrins and some nucleic bases or their nucleoside derivatives in aqueous solutions

Summary The mutual interactions of Gd(III)tetraphenylporphyrin (GdTPP), Gd(III)tetramethylpyridylporphyrin (GdTMePyP), and the free base tetramethylpyridylporphyrin (H₂ TMePyP) with some nucleic bases (adenine, thymine, uracil, and cytosine) and their N-glycoside derivatives (adenosine, thymidine, uridine, and cytidine) have been studied by spectrophotometric titration in mixed methanol-ammonia-water solutions. It has been found that tetramethylpyridylporphyrin and its gadolinium complex form 1:1 complexes with nucleic bases and their nucleoside derivatives. The equilibrium constants were estimated using curve fitting procedures. The interactions are stronger for nucleoside derivatives than for nucleic bases. They are also stronger for metallated than for non-metallated porphyrins.

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Komplexbildung zwischen Gadolinium(III)porphyrinen und einigen Nucleinbasen oder ihren Nucleosidderivaten in wäßrigen Lösungen

Zusammenfassung Die Wechselwirkungen von Gd(III)tetraphenylporphyrin (GdTPP), Gd(III)-tetramethylpyridylprophyrin (GdMePyP) und der freien Base Tetramethylpyridylporphyrin (H₂ TMePyP) mit einigen Nucleinbasen (Adenin, Thymin, Uracil, Cytosin) und ihren N-glycosidierten Derivaten (Adenosin, Thymidin, Uridin, Cytidin) wurden in Methanol-Ammoniak-Wasser — Mischungen mittels spektrophotometrischer Titration untersucht. Tetramethylpyridylporphyrin und sein Gadoliniumkpomplex bilden 1:1-Komplexe mit Nucleinbasen und ihren Nucleosidderivaten. Die Gleichgewichtskonstanten wurden übercurve-fitting - Algorithmen bestimmt. Die Wechselwirkungen sind für Nucleosidderivate stärker als für Nucleinbasen und für metallierte Porphyrine stärker als für nichtmetallierte.

     

Dual facet of gold(III) in the reactions of gold(III) and porphyrins

We have firstly demonstrated the dual facet of gold(III) in the reaction between gold(III) and porphyrins, which could be tuned through changing the counter ions, ligands and the electronic effect of the substituents of the porphyrins.     

Synthesis and spectral studies of gold(III) complexes with guanidine derivatives

New trivalent gold (d⁸ electronic configuration) halide complexes with guanidino–pyrimidines have been synthesized and delineated. The complexes have been identified and characterized by elemental analysis, u.v.–vis. electronic absorption spectra, i.r. oscillation spectra and by ¹H-n.m.r. and ¹³C-n.m.r. spectra. All substituted guanidine ligands in these chelates form part of a six-membered pseudo-heterocyclic ring where the nitrogen atoms of the guanidine group and the nitrogen atom of pyrimidine, piperidine or the morpholine heterocyclic ring bond to the metal.     

Spectroscopic and voltammetric study on the binding of aluminium(III) to DNA.

Cyclic voltammetry (CV) and ultraviolet (UV) spectroscopy were used, for the first time, to study the interaction between aluminium(III) and calf thymus DNA under neutral pH conditions. Thus obtained data confirmed the existence of a relatively strong interaction between Al(III) and DNA. The binding site for aluminium(III) on DNA chains is not the bases, but the phosphate groups on the DNA backbones, the same as that for [Co(phen)3](3+/2+) that binds non-specifically and electrostatically to the deoxyribose phosphate backbone of DNA. When coexisting, Al(III) binds more favorably to DNA than [Co(phen)3](3+/2+), which implies the relatively strong binding of Al(III) to the phosphate backbone of DNA under neutral pH conditions. The nature of the binding of Al(III) to DNA is also discussed.     

Organometallic gold(III) and gold(I) complexes as catalysts for the 1,3-dipolar cycloaddition to nitrones: synthesis of novel gold-nitrone derivatives

Gold(III) and gold(I) anionic salts mediate the 1,3-dipolar cycloaddition of N-benzyl-C(2-pyridyl)nitrone (2-PyBN) (1) and methyl acrylate (2) (gold 5-10 mol% with respect to the nitrone) decreasing the reaction time and favouring the formation of the exo (cis) isomer. The best catalyst found was Na[AuCl₄] (7) able to perform the addition reaction in 56 h (instead of the 96 h required for the control experiment) and giving an endo/exo relation between isomers of 44/56 (as opposed to 73/27, blank reaction). The catalytic activity of several organometallic gold complexes with the radicals pentafluorophenyl (C₆F₅) or mesityl (2,4,6-(CH₃)₃C₆H₂) has been also investigated. In some cases the activity is very similar to that obtained with inorganic salts. With the aim of identifying possible metallic intermediates in the cycloaddition reaction, novel gold(III) and gold(I) nitrone derivatives such as [Au(C₆F₅)Cl₂(2-PyBN)] (21), [Au(C₆F₅)₂Cl(2-PyBN)] (22) and [Au(C₆F₅)(2-PyBN)] (23) have been prepared and characterized. The reaction between [AuCl₃(tht)] and 2-PyBN unexpectedly affords the ionic compound [2-PyBN-H][AuCl₄] (5) which also displays catalytic activity and moderate regioselectivity and whose crystal structure has been confirmed by X-ray studies.     

Synthesis, crystal structure and thermal behavior of dimethylgold(III) derivatives of salicylaldimine Schiff bases - Novel precursors for gold MOCVD applications

Dimethylgold(III) complexes with salicylaldimine Schiff bases of general formula Me₂Au(SalN-R) (R = methyl (1), iso-propyl (2), or cyclohexyl (3)) have been synthesized in a single step reaction from dimethylgold(III) iodide [Me₂AuI]₂ and N-substituted salicylaldimines. Single-crystal X-ray studies provide evidence of mononuclear four-coordinated complexes with square-planar coordination geometry. The temperature dependences of saturated vapour pressure of complexes have been studied by the Knudsen effusion method with mass spectrometric analysis of the composition of the gas phase. The thermodynamic parameters of the sublimation process ΔH^o_T and ΔS^o_T have been calculated. Thermal decomposition of the vapour of compounds has been studied by means of high temperature mass spectrometry in a vacuum, and by-products have been determined. All of these complexes show good volatility and thermal stability. For complex 2, which is more volatile and low-melting, pulse MOCVD experiments have been carried out at substrate temperatures lower than 200 °C. The deposited gold nanoparticles (5-15 nm) have been investigated by means of SEM and AFM.     

Thermal decomposition mechanism of dimethyl(acetylacetonato)gold(III): Quantum chemical modeling

Different mechanisms of the thermal decomposition of the complex [(CH₃)₂Au(acac)] and the subsequent formation of Au particles are considered using density functional theory. The first decomposition step is the intramolecular reductive elimination of the methyl groups yielding ethane and the complex [Au(acac)], which dimerizes into the dinuclear complex [Au₂(acac)₂] with an energy gain. The presence of the coordinatively unsaturated center [Au(acac)] results in a considerable decrease in the activation energy of decomposition of the complex [(CH₃)₂Au(acac)]. The [Au₂(acac)₂] dimer undergoes association, again with an energy gain, to form linear polymer chains with short Au-Au bonds, which act as the nanoparticle nucleation centers.     

Ruthenium(III) complexes with tetradentate Schiff bases containing triphenylphosphine or triphenylarsine

Ruthenium(III) complexes of Schiff bases derived from the condensation of salicylaldehyde or o-vanillin with diamines have been prepared and characterised. The complexes are of the type [RuX(EPh₃)(L)] [X=Cl or Br; E=P or As; L=bis(salicylaldehyde)tetramethylenediimine, bis(salicylaldehyde)o-phenylenediimine, bis(o-vanillin)ethylenediimine, bis(o-vanillin)propylenediimine, bis(o-vanillin)tetramethylenediimine or bis(o-vanillin)o-phenylenediimine]. The Schiff bases behave as dibasic tetradentate ligands.     

Synthesis,characterization, interactions with DNA and bovine serum albumin (BSA), and antibacterial activity of cyclometalated iridium(III) complexes containing dithiocarbamate derivatives

Three mononuclear cyclometalated iridium(III) complexes having dithiocarbamate ligands, [Ir^III(2-C₆H₄py)₂(L)] (where 2-C₆H₄py?=?2-phenylpyridine; and L¹H?=?4-MePipzcdtH, L²H?=?MorphcdtH, and L³H?=?4-BzPipercdtH for 1, 2, and 3, respectively), were synthesized from [Ir(2-C₆H₄py)₂Cl]₂·1/4CH₂Cl₂ by displacing the two bridging chlorides with one dithiocarbamate ligand. The complexes were characterized using physicochemical and spectroscopic tools along with structural analysis of [Ir(2-C₆H₄py)₂(L²)] (2) by single crystal X-ray diffraction. Structural analysis of 2 showed a distorted octahedron in which the nitrogen donor of one 2-phenylpyridine and the carbon donor of another 2-phenylpyridine are in axial positions, trans to one another. Electrochemical analysis by cyclic voltammetry showed the irreversible two-electron equivalent reduction voltammograms of 1, 2, and 3 attributable to Ir(III) to Ir(I). Electronic characterizations of these complexes are consistent with significant delocalization of the sulfur electron density onto the empty metal d-orbital. The intercalative interaction of the complexes with calf thymus DNA was evaluated using absorption, fluorescence quenching, and viscosity measurements. The binding affinities of these complexes with bovine serum albumin were estimated in terms of quenching constants using the Stern–Volmer equation. Study of antibacterial activities of the complexes by agar disk diffusion against some species of pathogenic bacteria was also performed.     

Ruthenium(III) triazacyclononane dithiocarbamate,pyridinecarboxylate, or aminocarboxylate complexes as scavengers of nitric oxide

The preparation of a series of [Ru(III)(tacn)(eta(2)-dtc)(eta(1)-dtc)][PF(6)] (tacn = 1,4,7-triazacyclononane; dtc = dimethyldithiocarbamate, diethyldithiocarbamate, pyrrolidinedithiocarbamate, l-prolinedithiocarbamate, l-prolinemethyl ester dithiocarbamate, l-N-methylisoleucinedithiocarbamate) complexes, 5-11, is described. Complex 5 reacts with NO to form the ruthenium nitrosyl complex 12. A series of [Ru(III)(tacn)(pyc)Cl][PF(6)] (pyc = 2-pyridinecarboxylic acid, 2,4- and 2,6-pyridinecarboxylic acid) complexes, 14-16, were prepared along with [Ru(III)(tacn)(mida)][PF(6)] (mida = N-methyliminodiacetic acid), 13, and [Ru(III)(Hnota)Cl], 17, (Hnota = 1-acetic acid-4,7-bismethylcarboxylate-1,4,7-triazacyclononane). Complexes 5-17 were evaluated for use as NO scavengers in an in vitro assay using RAW264 murine macrophage cells. [Ru(III)(tacn)(eta(2)-dtc)(eta(1)-dtc)][PF(6)] complexes 5-11 are very efficient NO scavengers in this assay.