Synthesis, characterization and molecular structure of 1,1′ bis (diphenyl phosphino ferrocene) dioxide complex of the cis-uranyl dichloride

A 1,1' bis(diphenyl phosphino ferrocene) dioxide complex of the uranyl dichloride was synthesized and characterized by elemental analysis, H-1, P-31{H-1} NMR and X-ray diffraction methods. The structure of the compound shows that the uranium(VI) ion is surrounded by four oxygen and two chlorine atoms in an octahedral geometry. Two oxygen atoms from the bis (diphenyl phosphino ferrocene) dioxide and two chlorine atoms form a square planar arrangement. Two uranyl oxygen atoms occupy the axial positions. The bis(diphenyl phosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 82.90(16)degrees around the uranyl group. The two chlorine atoms are mutually cis with a CI-U-Cl angle of 97.75(7)degrees.

Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.

Preparation and characterization of new glassy system As2P2S8-Ga2S3

Glasses having the composition (100 - x)As2P2S8-xGa(2)S(3) with x ranging from 0 to 50% were investigated to determine the compositional effect on properties and local structure. The glass transition temperature (T-g) and the stability parameter against crystallization (T-x - T-g) increased with the addition of Ga2S3. The structure of these glasses was probed by Raman scattering, Fourier transform infrared (FT-IR) and P-31 nuclear magnetic resonance. On the basis of the observed vibrations and the strength of the P-31-P-31 homonuclear magnetic dipolar coupling, two scenarios can be proposed for the structural evolution induced by the addition of Ga2S3. For x <= 20% we may have the formation of GaS4E- groups (E = nonbonding electron), and for x >= 30% we have depolymerization of the As2P2S8 units and the formation of a network of GaPS4 units with each PS4/2 unit (Q(4)) species carrying a single positive formal charge.

Novel manganese (III) porphyrin containing peripheral [RuCl(dppb)(X-bipy)](+) cations [dppb=1,4-bis(diphenylphosphino) butane and X = -CH3, -OMe, -Cl]. X-ray structure of the cis-[RuCl(dppb)(bipy)(4-Mepy)]PF6 complex

New tetraruthenated manganese (III) porphyrins were synthesized and characterized (P-31 NMR, cyclic voltammetry, UV-Vis). This new system presents four units of cationic ``[RuCl(dppb)(X-bipy)](+)``. The electrochemical and catalytic properties of the central manganese (III) show dependence on the characteristics of the peripheral ruthenium complexes as evidenced by the Mn-(III)/Mn-(II) reduction potential. The catalytic oxidation reactions of olefins, cyclohexene and cyclohexane, were carried out in the presence of tetrapyridyl manganese (III) porphyrins containing cationic ruthenium complex and using iodosylbenzene as oxygen donor. The performance of these new tetraruthenated porphyrins systems were evaluated and compared with the manganese porphyrin. (C) 2007 Elsevier Ltd. All rights reserved.

Fluorescent AlPO(4) gels and glasses doped with Rhodamine 6G: Preparation, structural and optical characterization

Fluorescent AlPO(4) xerogels doped with different amounts of Rhodamine 6G (Rh6G) laser dye were prepared by a one-step sal-gel process. In addition, mesoporous AlPO(4) glasses obtained from undoped gels were loaded with different amounts of Rh6G by wet impregnation. Optical excitation and emission spectra of both series of samples show significant dependences on Rh6G concentration, revealing the influence of dye molecular aggregation. At comparable dye concentrations the aggregation effects are found to be significantly stronger in the gels than in the mesoporous glasses. This effect might be attributed to stronger interactions between the dye molecules and the glass matrix, resulting in more efficient dye dispersion in the latter. The interaction of Rh6G with the glassy AlPO(4) network has been probed by (27)Al and (31)P solid-state NMR techniques. New five- and six-coordinated aluminum environments have been observed and characterized by advanced solid-state NMR techniques probing (27)Al-(1)H and (27)Al-(31)P internuclear dipole couplings. The fractional area of these new Al sites is correlated with the combined fractional area of two new Q(3Al)((0)) and Q(2Al)((0)) phosphate species observed in the (31)P MAS NMR spectra. Based on this correlation as well as detailed composition dependent studies, we suggest that the new signals arise from the breakage of Al-O-P linkages associated with the insertion process. (C) 2010 Elsevier B.V. All rights reserved.

On the synthesis and structures of the complexes [RuCl(L)(dppb)(N-N)]PF(6) (L = CO, py or 4-NH(2)py; dppb=1,4-bis(diphenylphosphino)butane; N-N=2,2 `-bipyridine or 1,10-phenanthroline) and [(dppb)(CO)Cl(2)-Ru-pz-RuCl(2)(CO)(dppb)] (pz = pyrazine)

The ""Ru(P-P)"" unit (P-P = diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl(2)Ru-pz-RuCl(2)(CO)(dPPb)] (pz = pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N-N)]PF(6) (N-N = diimine). Complexes with the formula (RuCl(py)(dppb)(N-N)]PF(6) were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl(2)(dppb)(N-N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and (31)P{(1)H)} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. (C) 2010 Elsevier Ltd. All rights reserved.

Local Structure and Photochromic Response in Ormosils Containing Dodecatungstophosphoric Acid

Two hybrid materials based on dodecatungstophosphoric acid (HPW) dispersed in ormosils modified with 3-aminopropiltrietoxysilane (APTS) or with N-(3-(trimethoxysilyl)-propyl)-ethylene-diamine (TSPEN) show reversible photochromic response induced by irradiation in the 200-390 nm UV range. A set of solid-state nuclear magnetic resonance (NMR) techniques was used to analyze the structural properties of the main components of these hybrids (the HPW polyanion, the inorganic matrix, and the organic functionalities). For the ormosils, the use of (29)Si NMR, {(1)H}-(29)Si cross-polarization, and {(1)H}-(29)Si HETCOR revealed a homogeneous distribution of silicon species Q ``, T(2), and T(3) for the APTS hybrid, contrasting with the separation of T(3) species in the TSPEN hybrid. The combination of (31)P NMR, {(1)H}-(31)P cross-polarization and (31)P-{(1)H} spin-echo double resonance (SEDOR) revealed the dispersion of the HPW ions in the ormosil, occupying sites with a high number of close protons (>50). Differences in the molecular dynamics at room temperature, inferred from SEDOR experiments, indicate a state of restricted mobility of the HPW ion and the surrounding molecular groups in the TSPEN hybrid. This behavior is consistent with the presence of more amino groups in the TSPEN, acting as chelating groups to the HPW ion. This hybrid, with the strong chelate interaction of the diamine group, shows the most intense photochromic response, in agreement with the charge transfer models proposed to explain the photochromic effect. Electronic reflectance spectroscopy in irradiated samples revealed the presence of one-electron and two-electron reduced polyanions. The one-electron reduced species could be detected also by (31)P NMR spectroscopy immediately after UV irradiation.

Structure and antimycobacterial activity of the novel organometallic [Pd(C-bzan)(SCN)(dppp)] compound

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Studies on the encapsulation of diclofenac in small unilamellar liposomes of soya phosphatidylcholine

The encapsulation of acid (AD) and sodium diclofenac (SD) in small unilamellar liposomes (SUV) as well as the interactions of the drug with the bilayer was studied. SUV was prepared by sonication from multilamellar liposomes containing soya phosphatidylcholine and diclofenac at various proportions. The size distribution obtained from dynamic light scattering showed that the incorporation of SD decreases significantly the size of the liposomes suggesting that the drug interacts with the bilayer of the liposomes. This size decrease is related with the phase transition of liposomes to mixed micelar solution. The encapsulation of the hydrophilic dye indocyanine green in the aqueous compartment of liposomes showed that the rate of captured dye decreases with SD concentration suggesting the transition of liposomes to mixed micelles. The P-31 NMR analysis indicates that SD interacts with the phosphate of phosphatidylcholine head groups. A schematic model for interaction of SD with phosphatidylcholine of the liposomes in which the diclofenac anion interacts with the ammonium group of the phospholipid and the dichloropheryl ring occupies a more internal site of bilayer near phosphate group was proposed. (C) 2004 Elsevier B.V. All rights reserved.

Modeling a system of phosphated cross-linked high amylose for controlled drug release. Part 1: Synthesis and polymer characterization

High amylose was cross-linked with sodium trimetaphosphate (STMP) using 2% and 4% solutions of NaOH at room temperature with reaction contact times of 0.5, 1, 2 and 4 h. The different polymers obtained were analyzed by FT IR, C-13 and P-31 solid state NMR, SEM and C, H and P elemental analysis. The results were used to propose a two-stage mechanism for phosphate incorporation, the first being kinetically controlled. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, electrochemical behavior and X-ray crystal and molecular structures of [Fe(diene)(CO)(2)PPh3] (diene = chalcone, sorbic acid)

The compounds [Fe(ch)(CO)(2)PP3] (1) (ch = chalcone) and [Fe(sba)(CO)(2)PPh3] (2) (sba = sorbic acid) were prepared by irradiating the tetracarbonyltriphenylphosphineiron(0) complex in benzene in the presence of ch or sba. The compounds were characterized by infrared and P-31 NMR spectroscopies. Their electrochemical behavior was investigated by cyclic voltammetry and the results suggest that their oxidations occur by more than one electrochemical step, producing free ch and sba, free PPh3 and solvated Fe(III). It was observed that sba ligand contributes more effectively to the stabilization of metal center in these complexes, the X-ray crystal and molecular structures of 1 and 2 were determined; it was shown that the Fe atom adopts a distorted octahedral coordinated geometry in which three of the sites are occupied by the ch or sba ligand. The [Fe(ch)(CO)(2)PPh3] complex is a monomer and the unit cell of complex 2 contains exist two identical and crystallographically independent molecules of [Fe(sba)(CO)(2)PPh3] which are linked by short hydrogen bonds O-H . . .O (C) 2001 Published by Elsevier B.V. Ltd.

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.

Scandium fluorophosphate glasses: a structural approach

A systematic investigation on glass formation in the ternary system InF3-BaF2-[Sc(PO3)(3)](n) has been carried out. Scandium polyphosphate [Sc(PO3)(3)](n) has been used as a third component in order to investigate the possibilities of obtaining new stable glasses. The above long-chain polyphosphate has been prepared using a specially elaborated cryo-technique, which allowed the preparation of high-purity product. Stable ternary compositions have been obtained within the compositions range (in mol%): 5-75 InF3, 0-80% BaF2, 0-50% [Sc(PO3)(3)](n). Glasses were characterized by Differential Scanning Calorimetry, vibrational spectroscopy (Raman) and P-31 NMR. Structural features for the glass were put forward. Isolated P(O,F)4 groups or fluoroindated metaphosphate units could be identified depending on glass compositions. (C) 2002 Academie des sciences / Editions scientifiques et medicales Elsevier SAS.

Structural organization and thermal properties of the Sb2O3-SbPO4 glass system

The structural organization of Sb2O3-SbPO4 glasses has been studied by FTIR, Raman, P-31 MAS and spin echo NMR, Mossbauer and X-ray absorption spectroscopy (EXAFS and XANES at K and L-3,L-1-Sb edges). The combined results can be explained in terms of two potential mechanisms describing the change of the Sb(m) local environment upon incorporation of Q((4))-type phosphate. The formation of the latter species requires anionic compensation that may be adjusted by (a) formation of non bridging oxygen or (b) formation of SbO4E- groups (E = non-bonding electron pair). The second model is favored.

Thermal characterization of bacterial cellulose-phosphate composite membranes

Cellulose-phosphate composite membranes have been prepared from bacterial cellulose membranes ( BC) and sodium polyphosphate solution. The structure and thermal behavior of the new composites were evaluated by X-ray diffraction (XRD), P-31-nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG) and thermomechanical analysis (TMA). From XRD analyses the I alpha and I beta cellulose crystalline phases were identified together with crystalline sodium phosphate that covers the cellulose microfibrils as revealed by SEM. P-31 NMR spectra show peaks assigned to Q(0) and Q(1) phosphate structures to be compared to the Q(2) units that characterize the precursor polyphosphate. Glass transition temperature, T-g, obtained from TMA curves and thermal stability obtained from TG and DSC measurements, were observed to be dependent on the phosphate content.