(5,10,15,20-Tetra(4-pyridil)porphinato)manganes(III) acetate modified by four mu(3)-oxo-triruthenium acetate clusters: synthesis, characterization, electrochemical behavior and catalytic activity

A novel supermolecule constituted by four mu(3)-oxo-triruthenium acetate clusters coordinated to manganese(III)-meso -tetra(4-pyridil)porphyrin acetate ([MnTPyP]CH3COO) has been synthesized. Characterization has been performed by UV-Vis and H-1 NMR spectroscopy. The electrochemical behavior (cyclic voltammetry and spectroelectrochemistry) in N,N'-dimethylformamide has been analyzed in terms of five redox processes: three related to peripheral clusters (Ru-IV,Ru-III,Ru-III/Ru-III,Ru-III,Ru-III/Ru-III,Ru-II,Ru-II) and two centered on the Mn-porphyrin core ((MnP)-P-III/(MnP)-P-II/(MnP2-)-P-II). A direct comparison has been performed between MnTCP and MnTPyP as catalysts for the cyclooctene and cyclohexane oxidation reactions. The improved selectivity exhibited by the supramolecular catalyst for cyclohexane oxidation has been ascribed to electronic effects on the oxomanganese(V) porphyrin species induced by the four peripheral clusters, in the formal (RuRuRuIII)-Ru-IV-Ru-III oxidation state. (C) 2000 Elsevier B.V. S.A. All rights reserved.

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.

THERMAL ANALYSES OF COORDINATION-COMPOUNDS .2. THERMAL-DECOMPOSITION OF PALLADIUM COMPLEXES WITH TRIPHENYLPHOSPHINE, TRIPHENYLARSINE AND TRIPHENYLSTIBINE

The compounds [PdCl(2)L(2)] and [PdL(4)] (L=PPh(3), AsPh(3), SbPh(3)) were studied by thermogravimetric and differential thermal analyses in air. The residues of thermal decomposition consist of metallic palladium, except in the case of the complexes containing SbPh(3), when the residues are palladium and antimony mixtures in appropriate proportions with respect to the stoichiometry of the related complexes.

Small angle X-ray scattering and IR spectroscopy study of metal carbonyl complexes immobilized on a silica gel surface chemically modified with piperazine

The carbonyl complexes [WCl(CO)(3)(bipy) (HgCl)] (1), [Fe(CO)(4)(HgCl)(2)] (2) and W(CO)(6)] (3) were immobilized on a silica gel surface organofunctionalized with piperazine groups. The products obtained were studied by IR spectroscopy and small angle X-ray scattering (SAXS) techniques. The IR data show that the immobilization of heterobimetallic compounds 1 and 2, on the functionalized surface, occurred through the mercury atom, while for 3 the displacement of one CO group by the nitrogen of a piperazine molecule was observed. The data obtained from SAXS indicate that particles have a uniform size and reveal suitable modifications on the functionalized surface after immobilization of metal carbonyl complexes. The average intermolecular distance (l(ij)) for piperazine ligands on support is 8.7 Angstrom, for the metal carbonyl complex 1 it is 18.8 Angstrom, for complex 2 it is 16.2 Angstrom and for complex 3 it is 15.3 Angstrom. Copyright (C) 1996 Elsevier B.V. Ltd

Study of the alkaline earth metals with 8-hydroxyquinolinate derivatives - Calcium complexes

Metal complexes of calcium with 5,7-dibromo, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinolate were precipitated in aqueous ammonia and acetone medium, except for the solid state compound with 5,7-dichloro-8-hydroxyquinoline which hasn't been obtained under these conditions. The complexes obtained through the mentioned precipitation are Ca[(C9H4ONBr2)(2)](3).H2O, Ca[(C9H5ONI)(2)].2H(2)O and Ca[(C9H4ONICl)(2)].2.5H(2)O. Their intermediate from the thermal decomposition found through TG/DTA curves in air indicated the presence of different kinds of calcium carbonates related to the reversibility and crystalline structure, depending on the original compounds. The initial compounds and the intermediate from the thermal decomposition were also characterized through IR spectra and X-ray diffraction.

Study on the thermal behavior of the complexes of the type [PdX2(tdmPz)] (X = Cl-, Br-, I-, SCN-)

Four new mononuclear Pd(II) complexes of the type [PdX2(tdmPz)] {X = Cl- (1); Br- (2); I- (3); SCN- (4); tdmPz = 1-thiocarbamoyl-3,5-dimethylpyrazole} have been synthesized and characterized by elemental analysis, IR spectroscopy, H-1 and C-13{H-1}-NMR experiments. The thermal behavior of the complexes 1-4 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: 3 < 4 a parts per thousand 2 < 1. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.

Thermal study of mononuclear Pd(II) complexes of the type [Pd(X)(2)(Rtu)(PPh3)] (X = Cl, SCN; Rtu = N-methylthiourea, N-phenylthiourea)

The synthesis, spectroscopic characterization, and thermal analysis of the compounds [Pd(X)(2)(mtu)(PPh3)] (X = Cl- (1), SCN- (2); mtu = N-methylthiourea; PPh3 = triphenylphosphine) and [Pd(X)(2)(phtu)(PPh3)] (X = Cl- (3), SCN- (4); phtu = N-phenylthiourea) are described. The thermal decomposition of the compounds occurs in two, three, or four stages and the final decomposition products were identified as Pd-0 by X-ray powder diffraction. The thermal stability order of the complexes is 4 > 3 > 2 > 1.

Palladium(II) Complexes with Thiosemicarbazones. Syntheses, Characterization and Cytotoxicity against Breast Cancer Cells and Anti-Mycobacterium tuberculosis Activity

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

Mono and dinuclear Pd(II) complexes with pyrazole and imidazole-type ligands

The cyanate-bridged cyclopalladated compound [Pd(C(2),N-dmba)(mu-NCO)](2) (dmba=N,N-dimethylbenzylamine) reacts in acetone with pyrazole (pz), 3,5-dimethylpyrazole (dmpz), imidazole (imz) and 2-methylimidazole (mimz) to give [Pd(2)(C(2),N-dmba)(2)(mu-NCO)(mu-pz)] (1), [Pd(2)(C(2),N-dmba)(2)(mu-NCO)(mu-dmpz)] (2), [Pd(C(2),N-dmba)(NCO)(imz)] (3) and [Pd(C(2),N-dmba)(NCO)(mimz)] (4), respectively. The compounds were characterized by elemental analysis, IR spectroscopy and TG. The thermal decomposition of the compounds occurs in three consecutive steps and the final decomposition products were identified as Pd(0) by X-ray powder diffraction. The thermal stability order of the complexes is 2 > 3 > 1 > 4.

New chelate complexes of trivalent Y and lanthanides (Eu, Ho, Yb) with a triazene N-oxide: Synthesis, structural characterization and luminescence properties

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

NiBr2 complexes with triphenylarsine oxide (Ph3AsO). Two new interesting structures

The synthesis and crystal structure of two complexes resulting from interaction between NiBr2 and triphenylarsine oxide (Ph3AsO) is described. Green and orange complexes can be obtained from the blue, probably tetrahedral complex [NiBr2(Ph3AsO)2], depending on the solvents used for recrystallization. NiBr2·4[(C6H5)3AsO]·8H2O (green): M = 1650.2, P21/c, a = 13.731(2), b = 16.267(3), c = 17.647(2) Å, β = 112.04(1)°, V = 3651.4 Å3, Z = 2, Dx = 1.501 g cm-3, CuKα, λ = 1.54184 Å, μ = 38.67 cm-1, R = 0.039, 3741 unique reflections, 3203 with I > 3σ(I). NiBr2·4[(C6H5)3AsO]·3|2(C6H5CH3)·H2O (orange): M = 1663.7, P1, a = 12.647(8), b = 13.953(5), c = 22.853(6) Å, α = 90.91(3), β = 96.70(4), γ = 111.16(4)°, V = 3727.4 Å3, Z = 2, Dx = 1.482 g cm-3, MoKα, λ = 0.71073 Å, μ = 30.48 cm-1, R = 0.087, 8600 unique reflections, 4293 with I > 3σ(I). In the green complex the Ni(II) ion is sited on a center of symmetry and is octahedrally coordinated to six water molecules, hydrogen bonded to the Ph3AsO molecules and to the bromide anions forming a second coordination sphere in a nearly octahedral arrangement. In the orange complex the cation is pentacoordinated with the four oxygen atoms of the Ph3AsO ligands forming the basis of a tetragonal pyramid and with one Br- anion in the apical position. The absorption spectrum of the orange complex is compared with the spectra of other Ni(II) square pyramidal complexes described in the literature. © 1984.

Spectroscopic studies on copper(II)triphenylarsine oxide square planar complexes

Electronic and ESR spectra of the complexes [Cu(II)(tpaso)4][Cu(I)Cl2]2,[Cu(tpaso)4](NO3)2 and [Cu(tpaso)4](ClO. © 1985.

Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

Synthesis, structure, and electronic and EPR spectra of copper(II) complexes containing the [CuBr4]2- anion and triphenylarsine oxide

The preparation and characterization of (Ph3AsOH)2[CuBr4] and [Cu(Ph3AsO)4][CuBr4] are reported (Ph3AsO = triphenylarsine oxide). Crystallographic analysis of the monoclinic crystals of (Ph3AsOH)2[CuBr4] (space group C2/c, a = 17.569 (3) Å, b = 13.090 (2) Å, c = 16.933 (2) Å, and β = 105.64 (2)°, R = 0.055 and Rw = 0.057) revealed the presence of compressed [CuBr4]2- tetrahedra of C2 symmetry with Cu-Br distances of 2.340 (1) and 2.437 (1) Å and trans-Br-Cu-Br angles of 139.2 (1) and 122.4 (1)°. The oxonium cations hydrogen bond to the bromine atoms involved in the longer Cu-Br bonds and the smaller trans-Br-Cu-Br angle. Single-crystal electronic and EPR spectra are interpreted in terms of the observed [CuBr4]2- geometry. Analysis of the electronic and EPR spectra of [Cu(Ph3AsO)4][CuBr4] led to the postulation of the presence of planar [Cu(Ph3AsO)4]2+ cations and distorted tetrahedral [CuBr4]2- anions. © 1992 American Chemical Society.

Phochemical behavior of trans-[Ru(NH3)4P(OEt)3L]2+ complex ions (L = P(OEt)3, CO, H2O)

trans-[Ru(NH3)4P(OEt)3H2O] 2+, trans-[Ru(NH3)4(P(OEt)3)]2+, and trans-[Ru(NH3)4P(OEt)3CO]2+ were photolyzed with light of 313 nm on the lowest energy ligand field excited state. Photoaquation of the thermally substitution inert ammonia is observed for all three complexes with φ ≅ 0.30 mol/einstein. trans-[Ru(NH3)4(P(OEt)3)2] 2+ undergoes P(OEt)3 photoaquation with φ ≅ 0.12 mol/einstein, while trans-[Ru(NH3)4P(OEt)3CO]2+ displays CO photoaquation with φ = 0.07 mol/einstein. The results suggest that the electronic configuration of the lowest energy excited state of these complexes have contributions from E and A2 states. Furthermore, in trans-[Ru(NH3)4P(OEt)3CO]2+ the photoaquation of CO is explained by depopulation of a bonding dπ orbital and population of a σ* orbital. © 1992 American Chemical Society.