Synthesis, characterization, X-ray structure and in vitro anti mycobacterial and antitumoral activities of Ru(II) phosphine/diimine complexes containing the "SpymMe(2)" ligand, SpymMe(2)=4,6-dimethyl-2-mercaptopyrimidine

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)

The binding selectivity of the M(phen)(edda) (M = Cu, Co, Ni, Zn; phen = 1,10-phenanthroline, edda = ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(11) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N4O2 octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling. (C) 2008 Elsevier B.V. All rights reserved.

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal Behavior of Sr(II) and Ba(II)-Diclofenac Complexes in Solid State: Study of the Dehydration and Thermal Decomposition

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermal behavior of copper(II) pseudohalide complexes containing bidentate amines

Pseudohalide complexes of copper(II) with aliphatic bidentate amines, [Cu(N-3)(2)(N,N-diEten)](2) 1, [Cu(NCO)(2)(N,N-diEten)](2) 2, [Cu(NCO)(2)(N,N-diMeen)](2) 3, [Cu(N-3)(NCS)(N,N'-diMeen)](2) 4 and [Cu(N-3)(NCO)(N,N-diMeen)](2) 5 (N,N-diEten=N,N-diethylethylenediamine; N,N-diMeen=N,N- dimethyl-ethylenediamine and N,N'-diMeen = N,N'-dimethylethylenediamine), were prepared, characterized and their thermal behavior was investigated by TG curves. According to thermal analysis and X-ray diffraction patterns all compounds decomposed giving copper(II) oxide as final product. The mechanisms of decomposition were proposed and an order of thermal stability was established.

Solution infrared spectroscopy investigation of copper (II) azide-complexes.

The structure of the two azide-complexes, [Cu(N-3)(2)(N,N-diEten)](2) and [Cu(N-3)(2)(tmeen)](2), N,N-diEten=N,N-diethylethylenediamine; tmeen=N,N,N',N'-tetramethyethylenediamine in solutions of acetonitrile, acetone, tetrahydrofuran, chloroform and dichloromethane, were investigated by infrared spectroscopy. The data show that the complex [Cu(N-3)(2)(N,N-diEten)](2) mantains its structure in solution, while that for [Cu(N-3)(2)(tmeen)](2) is modified.

Thermal decomposition of palladium(II) pyrazolyl complexes. Part I

The thermal behavior of simple and mixed pyrazolyl complexes [PdCl2(phmPz)(2)] (1),[Pd(N-3)(2)(phmPz)(2)] (2), [Pd(SCN)(2)(phmPz)(2)] (3), and [Pd(N-3)(SCN)(phmPz)(2)] (4) (phmPz: 1-phenyl-3-methylpyrazole) has been investigated by means of thermogravimetry (TG) and differential thermal analysis (DTA). From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 4 < 2 < 3 < 1. The final products of the thermal decompositions were characterized as metallic palladium (Pd-0). (C) 2004 Elsevier B.V. All rights reserved.

Mixed pseudohalide complexes of copper(II). Crystal and molecular structure of [Cu(N-3)(NCS)(tmen)](n) and of [Cu(N-3)(NCO)(tmen)]2 (tmen = N,N,N ',N '-tetramethylethylenediamine)

The compounds [Cu(N-3)(NSC)(tmen)](n) (1), [Cu(N-3)(NCO)(tmen)](n) (2) and [Cu(N-3)(NCO)(tmen)](2) (3) (tmen = N,N,N',N'-tetramethylethylenediamine) were synthesized and studied by i.r. spectroscopy. Single crystals of compounds (1) and (3) were obtained and characterized by X-ray diffraction. The structure of compound (1) consists of neutral chains of copper(II) ions bridged by a single azido ligand showing the asymmetric end-to-end coordination fashion. Each copper ion is also surrounded by the other three nitrogen atoms: two from one N,N,N',N'-tetramethylethylenediamine and one from a terminal bonded thiocyanate group. Compound (2) decomposes slowly in acetone and the product formed [Cu(N-3)(NCO)(tmen)](2) (3) crystallizes in the monoclinic system (P2(1)). The structure of (3) consists of dimeric units in which the Cu atoms are penta-coordinated and connected by p(1,3) bridging azido and cyanate ligands. In both cases the five coordinated atoms give rise to a slightly distorted square-based pyramid coordination geometry at each copper ion. The thermal behavior of [Cu(N-3)(NSC)(tmen)](n) (1) and [Cu(N-3)(NCO)(tmen)](n) (2) were investigated and the final decomposition products were identified by X-ray powder diagrams.

Self-assembly of Pd(II) pyrazolyl complexes to 1-D hydrogen-bonded coordination polymers

This work describes the synthesis and characterization of two novel Pd(II) pyrazolyl complexes of the type [PdX2(HdmPz)(2)](n) {X=SCN- (1), N-3(-) (2); HdmPz=3,5-dimethylpyrazole} that self-assemble through N-H...NCS or N-H...NNN hydrogen bonds to yield infinite one-dimensional chains, as confirmed by single crystal X-ray study on 1. The expected solid state polymeric structure for 2 is slowly broken up in CHCl3 Solution, leading to an equilibrium mixture of cis and trans-[Pd(N-3)(2)(HdmPz)(2)] monomers, as demonstrated by time-dependent IR and NMR studies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Oxidation of nickel(II) cyclam and tetraglycine complexes by dissolved oxygen in the presence of sulfur(IV). Synergistic effects of manganese(III) and cobalt(III)

The autoxidation of [Ni-II(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) and Ni(II)tetraglycine, accelerated by S-IV is studied spectrophotometrically by following the formation of Ni-III complexes.

Thermal studies on nickel(II) 4-iodopyrazole complexes

This work describes the synthesis, IR and UV-Vis spectroscopic characterization as well the thermal behavior of the [NiCl2(HIPz)(4)]center dot C3H6O (1), [Ni(H2O)(2)(HIPz)(4)](NO3)(2) (2), [Ni(NCS)(2)(HIPz)(4)] (3) and [Ni(N-3)(2)(HIPz)(4)] (4) (HIPz = 4-iodopyrazole) pyrazolyl complexes. TG experiments reveal that the compounds 1-4 undergo thermal decomposition in three or four mass loss steps yielding NiO as final residue, which was identified by X-ray powder diffraction.

Structure characterization of molecular complexes for non-linear optical materials. II. 1 : 1 complexes of 4-methyl-morpholine-N-oxide (1) and 3-picoline-N-oxide (2) with 2,4,6-trinitrophenol, studied by X-ray, AM1 and DFT calculations

(1) C6H2N3O7- center dot C5H12NO2+, Mr = 346.26, P2(1)/c, a = 7.2356(6), b = 10.5765(9), c = 19.593(2) angstrom, 3 beta=95.101(6)degrees, V = 1493.5(2) angstrom(3), Z = 4, R-1 = 0.0414; (2) C6H2N3O7- center dot C6H8NO+, Mr = 38.24, P2(1)/n, a = 7.8713(5), b = 6.1979(7), c = 28.697(3) angstrom, beta = 90.028(7)degrees, V = 1400.0(2) angstrom(3), Z = 4, R-1 = 0.0416. The packing units in both compounds consist of hydrogen bonded cation-anion pairs. The (hyper)polarizabilities have been calculated for the crystallographic and optimized molecules, by AM1 and at the DFT/B3LYP(6-31G**) level.

Luminescence of europium(III) and manganese(II) in barium and zinc orthosilicate

The aim of this work is to report on the luminescence properties of BaZnSiO4 activated by Eu3+ and Mn2+ ions. Doped and undoped powder samples were prepared by solid-state reaction starting from oxides and carbonates or Ba2SiO4:Eu3+ and Zn2SiO4:Mn2+ precursors. X-ray diffraction powder data, IR vibrational, and UV-vis luminescence spectroscopies were carried out. Results showed that doped and undoped samples from both types of precursors have the same structure and crystallize with a superstructure of hexagonal kalsilite. Vibrational spectroscopy has confirmed the formation of a silicate group, which outlines differences between products and silicate precursors. The observed luminescence assigned to Eu3+ and Mn2+ transitions covered most parts of the visible spectrum, an important requirement for phosphors in fluorescent low-pressure mercury vapor lamps.

New Ni(II)-sulfonamide complexes: Synthesis, structural characterization and antibacterial properties. X-ray diffraction of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)]

The synthesis, structural characterization, voltammetric experiments and antibacterial activity of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] were studied and compared with similar previously reported copper complexes. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O crystallized in a monoclinic system, space group C2/c where the nickel ion was in a slightly distorted octahedral environment, coordinated with two sulfisoxazole molecules through the heterocyclic nitrogen and four water molecules. [Ni(sulfapyridine)(2)] crystallized in a orthorhombic crystal system, space group Pnab. The nickel ion was in a distorted octahedral environment, coordinated by two aryl amine N from two sulfonamides acting as monodentate ligands and four N atoms (two sulfonamidic N and two heterocyclic N) from two different sulfonamide molecules acting as bidentate ligands. Differential pulse voltammograms were recorded showing irreversible peaks at 1040 and 1070 mV, respectively, attributed to Ni(II)/Ni(III) process. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] presented different antibacterial behavior against Staphylococcus aureus and Escherichia coli from the similar copper complexes and they were inactive against Mycobacterium tuberculosis. (c) 2007 Elsevier B.V. All rights reserved.