Energy of the Photosubstitutionally Reactive Excited State of Pentaammine(pyridine)ruthenium(II)

The photosensitized aquation of pentaammine(pyridine)ruthenium(II) by several dyes has been studied under conditions where only the sensitizers absorb light. The ratio of the quantum yields for ammine and pyridine substitution was the same as that for direct photoaquation. Sensitization was effective with singlet sensitizers Rhodamine-B (17 452 cm -1) and Safranine-T (17 690 cm -1), as well as the triplet sensitizer biacetyl (19 000 cm -1), but no reaction was observed with Neutral-Red (16 900 cm -1). The results indicate that the excited state precursor of the observed photosubstitution in the complex lies in the energy range between 17 000 and 17 700 cm -1.

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson's disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)(5)Ru-III-O-Ru-IV(NH3)(4)-O-Ru-III(NH3)(5)](6+) (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2 x 10(-4) and 1.0 x 10(-2) Mol l(-1) (r = 0.9988) with a detection limit of 8.5 x 10(-5) mol l(-1). The variation coefficient for a 1.0 x 10(-3) mol l(-1) L-dopa (n = 10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. (C) 2004 Elsevier B.V. All rights reserved.

Langmuir and Langmuir-Blodgett films containing a porphyrin-ruthenium complex

The fabrication of supramolecular structures from the tetraruthenated porphyrin-containing phosphines, {TPyP[RuCl3(dppb)](4)}, RuTPyP, is demonstrated with Langmuir and Langmuir-Blodgett films. The surface pressure-molecular area isotherms (pi-A) point to an edge-on arrangement for the RuTPyP molecules in the condensed state. Weak aggregation in the Langmuir films was indicated by non-zero surface potentials at large areas per molecule and a slight red shift in the ultraviolet-visible absorption spectrum in comparison to the spectrum in solution. Further aggregation occurs in the Z-type Lang muir-Blodgett films, which was confirmed with ultraviolet-visible spectroscopy of the deposited films. Fourier transform infrared and Raman spectroscopic data for powder and Langmuir-Blodgett films indicate that the RuTPyP molecules are chemically stable in Langmuir-Blodgett films regardless of the contact with water during film fabrication. The nanostructured nature of the Langmuir-Blodgett films was manifested in cyclic voltammetry due to the high sensitivity of the metallic centers in RuTPyR Electrodes modified with Langmuir-Blodgett films exhibit an anodic peak at 100 mV and a cathodic peak at 7 mV, which is assigned to RuIII/RuII redox processes. Furthermore, Langmuir-Blodgett films from RuTPyP showed electrocatalytic activity for oxidation of benzyl alcohol, illustrated by a large shift of 100 mV in the anodic peak at 400 mV, while electropolymerized and cast films of the same compound displayed smaller and no activities, respectively.

Molecularly organized Langmuir-Blodgett films from a ruthenium biphosphine complex

Langmuir-Blodgett (LB) films from a ruthenium complex mer-[RuCl3 (dppb)(4-Mepy)] (dppb = PPh2 (CH2)(4)-PPh2; 4-Mepy = 4-methylpyridine), termed Ru-Pic, display a distinct color, which is different from the coloration exhibited by cast films or chloroform solutions. The solution and cast films are red, while the LB films are green-bluish. The manifestation of the blue color in the LB film finds its explanation in a unique absorption band at 690 nm, which is associated with the oxidation of the phosphine moieties. Fluorescence emission and absorption-reflection infrared spectroscopy measurements revealed the molecular organization in the LB films. In contrast, cast films showed a random distribution of complexes. Surface-enhanced Raman scattering was also used in an attempt to identify the main interactions in Ru-Pic.

Electrochemical investigation of the dimeric oxo-bridged ruthenium complex in aqueous solution and its incorporation within a cation-exchange polymeric film on the electrode surface for electrocatalytic activity of hydrogen peroxide oxidation

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

Ruthenium (II) phosphine/picolinate complexes as antimycobacterial agents

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)

Simultaneous Determination of Two Groups of Elements in Milk by Electrothermal Atomic Absorption Spectrometry: Evaluation of Ruthenium Modifiers

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

Electrosynthesis of binuclear ruthenium complexes from [RuCl3(dppb)(L)] precursors [L = pyridine, 4-methylpyridine or dimethyl sulfoxide; dppb=1,4-bis(diphenylphosphino)butane]

Electrolysis has been examined as a method of synthesis for [(L)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] complexes, where dppb = 1,4-bis(diphenylphosphino)butane and L = pyridine (py), 4-methylpyridine (4-pic) or dimethyl sulfoxide (DMSO), by using [RuCl3(dppb)(L)] as precursors. The products of the electrolysis were characterized by P-31-{H-1} NMR, cyclic voltammetry and near infrared spectroscopy. The presence of the [Ru2Cl5(dppb)(2)] complex in the electrochemical cell suggests a mechanism by which the starting original species from the bulk solution reacts with the reduced form [RuCl2(dppb)(L)] generated at the surface of the electrode. The crystal structure of the precursor mer-[RuCl3(dppb)(4-pic)] was determined by X-ray diffraction.

Preparation, characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex

Langmuir-Blodgett (LB) films from a ruthenium complex, mer-[RuCl3(dppb)(py)] (dppb = PPh2(CH2)(4)PPh2; py = pyridine) (Rupy), and from mixtures with varied amounts of polyaniline (PANi) were fabricated. Molecular-level interactions between the two components are investigated by surface potential, dc conductivity and Raman spectroscopy measurements, particularly for the mixed film with 10% of Rupy. For the latter, the better miscibility led to an interaction with Rupy inducing a decrease in the conducting state of PANi, as observed in the Raman spectra and conductivity measurement. The interaction causes the final film properties to depend on the concentration of Rupy, and this was exploited to produce a sensor array made up of sensing units consisting of 11-layer LB films from pure PANi, pure Rupy and mixtures with 10 and 30% of Rupy. It is shown that the combination of only four non-specific sensing units allows one to distinguish the basic tastes detected by biological systems, viz. saltiness, sweetness, sourness and bitterness, at the muM level. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

mer-[RuCl3(P-P)H2O] (P-P=dppb or diop) as a starting material for the synthesis of binuclear complexes. Crystallographic structures of [(dppb)ClRu-mu(Cl)(3)-RuCl(dppb)] and [(eta(6)-C6H6)Ru-mu(Cl)(3)-RuCl(dppb)]. Imine hydrogenation using mono- and binuclear ruthenium complexes

The reactivity of the mer-[RuCl3(dppb)H2O] complex (1) with di-hydrogen shows that the products formed depend on the conditions of the reaction, i.e., solvents and presence or absence of a base. The new mixed-valence complexes [(diop)ClRu-(h-Cl)(3)-RuCl(dppb)] (3), [(binap)CIRu-(p-Cl)(3)-RuCl(dppb)] (4), [(PPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (6), [(dppn)ClRu-(mu-Cl)(3)-RuCl(dppb)] (7), [(P-ptol(3))(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (8), [(SbPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (9), [(eta(6)-C6H6)Ru-(mu-Cl)(3)-RuCl(dppb)] (11) and the known mixed-valence [(dppb)CIRu-(mu-Cl)(3)-RuCl(dppb)] (5) and [(diop)ClRu-(mu-Cl)(3)-RuCl(diop)] (10) were synthesized from complexes (1) or (2) using a methodology developed in our research group. The known complexes [(dppb)ClRu-(mu-Cl)(2)-RuCl(dppb)] (12), [(dppb)(CO)Ru-(mu-Cl)(3)-RuCl(dppb)] (13) and [H2NEt2][(dppb)ClRu-(mu-Cl)(3)-RuCl(dppb)] (14) were synthesized by changing the reaction conditions between mer-[RuCl3(dppb)H2O] (1) and dihydrogen. The crystal structures of (5) and (11) were determined by single-crystal X-ray diffraction. Some of the complexes described here are effective pre-catalysts for the hydrogenation of imines. Preliminary results on the homogeneous hydrogenation of the imines Ph-CH2-N=CH-Ph and Ph-N=CH-Ph are presented. (C) 2004 Elsevier Ltd. All rights reserved.

Morphological characterization of Langmuir-Blodgett films from polyaniline and a ruthenium complex (Rupy): influence of the relative concentration of Rupy

We report on the use of dynamic scale theory and fractal analyses in a study of the growth stages of Langmuir-Blodgett (LB) films of polyaniline and a neutral biphosphinic ruthenium complex, namely mer-[ RuCl3 (dppb)(py)] (dppb = 1,4-bis(diphenylphosphine) buthane, py = pyridine), Rupy. The LB films were deposited onto indium-tin-oxide substrates and characterized with atomic force microscopy. From the granular morphology exhibited by the films one could infer growth processes inside and outside the grains. Growth outside was found to follow the Kardar-Parisi-Zhang model, with fractal dimensions of about 2.7. As one would expect, inside the grains the morphology is close to a Euclidian surface with fractal dimension of about 2.

Nitrosyl ruthenium complexes with general formula [RuCl3,(NO)(P-P)] (P-P={PPh(2)(CH2)(n)PPh(2)},n=1-3 and {PPh(2)-CH=CH-PPh(2)}). X-ray structure of [RuCl3(NO){PPh(2)(CH2)(3)PPh(2)}]

Ruthenium(II) complexes with general formula [RuCl3(NO)(P-P)] were obtained in the solid state, where P-P = PPh(2)(CH2)(n)PPh(2) (n = 1-3) and PPh(2)-CH = CH-PPh(2). The P-31 NMR spectra of these compounds measured in CH2Cl2 showed only singlets, consistent with a fac configuration containing two equivalent phosphorus atoms, However the X-ray diffraction data show that the [RuCl3(NO){PPh(2)(CH2)(3)PPh(2)}] complex crystallizes in a met configuration, where one of the phosphorus atoms is trans to the NO group, in a slightly distorted octahedral geometry. Copyright (C) 1996 Elsevier B.V. Ltd

A NOVEL SYNTHETIC ROUTE FOR SUPPORTING RUTHENIUM COMPLEXES ON FUNCTIONALIZED SILICA-GEL

The immobilization of the ruthenium moiety Ru(NH3)4SO3 by reaction of trans-[Ru(NH3)4SO2(H2O)]2+ with silica gel functionalized with 3-(1-imidazolyl)propyl groups is reported. A 60% surface coverage was obtained in the proportion of the resulting material [=Si(CH2)3imN-Ru(NH3)4SO3]. The anchored Ru(II) complex was characterized and its reactivity investigated. Derivatives of CO, pyrazine, and isonicotinamide have been prepared and characterized by electronic and vibrational spectroscopies, as well as by chemical means. The [=Si(CH2)3imN-Ru(NH3)4SO4]Cl, obtained through oxidation of the corresponding ruthenium(II) sulfite species, has been characterized and the aquo and the oxalate derivative have been synthesized.

Properties and one-step synthesis of (2-acetylpyridine)tetraammineruthenium(II), [Ru-II(2-acpy)(NH3)(4)](2+) and tetraammine(2-benzoylpyridine)ruthenium(II), [Ru-II(NH3)(4)(2-bzpy)](2+) Redox potentials, UV-Vis and NMR spectra

A more direct and efficient route to the syntheses of [Ru(NH3)(4)(X-Y)](BF4)(2), where X-Y can be 2-acetylpyridine (2-acpy) or 2-benzoylpyridine (2-bzpy), based on the reactions of [RuCl(NH3)(5)]Cl-2 with these ortho-substituted azines is described. The [Ru(2-acpy)(NH3)(4)](BF4)(2) and [Ru(NH3)(5)(2-bzpy)](BF4)(2) complexes have a molar conductance of 328 and 292 Ohm(-1) cm(2) mol(-1), respectively, corresponding to a 1:2 species in solution. These complexes showed two intense absorption bands around 620-650 and 380 nm, the energies of which are solvent dependent, decreasing with the increase of the Gutman's donor number of the solvent, and were assigned as metal-to-ligand charge transfer (MLCT). The complexes have oxidation potentials (Ru-II/III) of +0.380 V vs. Ag/AgCl (2-acpy) and +0.400 V vs. Ag/AgCl (2-bzpy), and reduction potentials (X-Y0/-) of -1.10 V vs. Ag/AgCl (2-acpy) and -0.950 V vs. Ag/AgCl (2-bzpy) on CF3COOH/NaCF3COO at pH=3.0, scan rate 100 mV s(-1), [Ru]=1.0x10(-3) mol l(-1). Both processes show a coupled chemical reaction. Upon oxidation of the metal center, the MLCT absorption bands are bleached and restored upon subsequent reduction. In order to confirm the structure of the complexes a detailed LH NMR investigation was performed in d(6)-acetone. Further confirmation of the structure was obtained by recording the N-15 NMR spectrum of [Ru(NH3)(4)(2-bzpy)](2+) in d(6)-DMSO using the INEPT pulse sequence improving the sensitivity of N-15 by polarization transfer from the protons to the N-15. The Nuclear Overhauser Effect (NOE) experiments were made qualitatively for [Ru(NH3)(4)(2-acpy)](2+), and showed that H-6 of the pyridine is close to a NH3 proton, which should then be in a cis position, and, hence, confirming that acpy is acting as a bidentate ligand. (C) 1999 Elsevier B.V. Ltd. All rights reserved.