Reactions of titanium(IV) isopropoxide with aliphatic and aromatic hydroxy esters,part I. 5-, 6-, 7- and 8-coordinate titanium(IV) complexes

Summary Reactions of titanium(IV) isopropoxide with ethyl 1-hydroxycyclohexylacetate, ethyl 2-hydroxy-2-arylpropionate, ethyl 2-hydroxy-2-arylbutyrate and ethyl 2-hydroxy-2-arylhydrocinnamate have been studied in dry benzene in different molar ratios under strictly anhydrous conditions. The Ti(OPr-i)₄-_nL_n type compounds, where L = hydroxy ester and n = 1 to 4, have been isolated and characterised by elemental analysis, molecular weight, i.r. and n.m.r. spectral studies. These products may be distilled unchanged under reduced pressure.Reprints of this are not available.     

Some new organotin(IV), aluminium(III)-μ-oxoisopropoxides and their benzoylacetone derivatives

The first organotin(IV), aluminium(III)-μ-oxoisoprovides of the type [R₃SnOA](OⁱPr)₂] (R = Me or Ph) have been made by heating of trimethyl- or triphenyl-tin acetate with aluminium isopropoxide. The reactions of these μ-oxoisopropoxides with benzoylacetone in 1:1 and 1:2 molar ratios yielded the compounds of the type [R₃SnOAl(OⁱPr)(bzac)] and [R₃SnOAl(bzac)₂] (where R = Me or Ph and BZAC = deprotonated benzoylacetone), respectively.     

Growth and reactivity of silver clusters in amino polycarboxylic acid solutions

Reduction and subsequent aggregation of silver ions in the presence of various chelating agents such as trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) 1,2-propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraaminehexaacetic acid (TTHA) have been studied by pulse radiolysis. Rate constants of formation and transient absorption spectra for the ligand-complexed Ag(0) and Ag(2)(+) have been determined. The redox potential of Ag(+)(L)/Ag(0)(L) becomes more negative than that of Ag(+)/Ag(0). Growth and reactivity of silver clusters were also studied in the presence of methyl viologen (MV(2+)). The kinetics of formation of the MV(+*) radical, produced by the same pulse as in the case of silver atoms, confirms the catalytic electron transfer toward super critical silver clusters in the presence of ligands. The results suggest that catalytic electron transfer activity of silver clusters depends on the ligand.     

Transition metal complexes with bidentate ligands spanning trans-positions. XII. The preparation and properties of complexes trans-[MX2 (1)] and trans-[PtHCl (1)] (M = Ni,Pd and Pt; X = Cl and NCS; 1 = ditertiary phosphine)

Complexes [MX₂(1)] (M = Ni, Pd and Pt; X=Cl and NCS; 1 = 2,11-bis(dialkyl-[or diaryl]phosphinomethyl)benzo[c]phenanthrene; alkyl = cyclohexyl t-butyl; aryl = m-tolyl, p-anisyl and m-CF₃ C₆H₄) have been synthesized. An NMR. study of the t-butyl complexes provides evidence for a “fan-like” motion of the benzo[c]phenanthrene moiety over the plane of the complex.     

Recovery of plutonium and americium from laboratory acidic waste solutions using tri-n-octylamine and octylphenyl-N-N- diisobutylcarbamoylmethylphosphine oxide

Plutonium from acidic waste solutions has been recovered quantitatively using tri-n-octylamine (TnOA) in xylene and americium using a mixture of octylphenyl-N-N- diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane by extraction and extraction chromatographic methods. The Pu ( IV ) TnOA species extracted into the organic phase from higher nitric acid concentrations has been confirmed as (R(3)NH)(2)Pu(NO(3))(6) (where R(3)N = TnOA by employing slope analysis as well as spectrophotometric studies.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Studies on adsorption of 5-amino tetrazole on silver nanoparticles by SERS and DFT calculations

The surface-enhanced Raman scattering (SERS) studies of 5-amino tetrazole (5AT), a tetrazole derivative, in aqueous silver sol at pH approximately 9 and on deposited colloidal silver films were carried out and compared with the normal Raman spectrum of the molecule. The experimentally observed Raman bands along with their corresponding infrared bands were assigned based on the results of density functional theory (DFT) calculations. The significant changes evidenced between the SERS and the normal Raman spectra combined with the theoretical data obtained for Ag-5AT system demonstrated that the molecule is adsorbed on colloidal Ag particles through the lone pair of electrons of the nitrogen atom. The contribution of the chemical mechanism for the SERS enhancement was proved by the behavior of the electronic absorption spectrum of the Ag colloid upon addition of 5AT. This is further supported by the theoretical calculations that show that the favorable interaction of the frontier orbitals localized on Ag(+) and the negatively charged nitrogen from the tetrazole ring leads to the formation of the stable (up to 130 kJ mol(-1)) charge-transfer complex. The orientation of the adsorbed species with respect to the metal surface was also predicted by applying the "surface selection rule". In addition, the feasibility of the formation of the polymeric species has also been discussed.     

Formulation–composition map of a lecithin-based emulsion

Formulation–composition map is an interesting tool to predict the nature of an emulsion, stability, viscosity and nevertheless to decide the mixing protocol of its ingredients. Information based on optimum formulation (environmental conditions at which the affinity of an emulsifier for oil and for aqueous phase is same), which is depicted through hydrophilic–lipophilic deviation (HLD) concept, is necessary to make a formulation–composition map of an emulsion. In order to apply this concept in food emulsions, it is necessary to determine characteristic constants of each component of the system, i.e. the aqueous phase, the oil phase and the emulsifier at equilibrium. In this work formulation–composition map of a sunflower oil–water–lecithin system, based on the knowledge of phase behavior of lecithin at equilibrium and emulsification, was made. The shape of inversion line on formulation–composition map was not the classical stair type rather an almost vertical inversion line at water-fraction (f_w) near 0.20 was observed. It was supposed to be linked to the viscosity of oil phase which was 50 times the viscosity of aqueous phase. Additionally, emulsions were of oil-in-water (O/W) type for f_w higher than 0.20, but their viscosity and the drop size behavior with respect to salt concentration as formulation variable did not show the existence of transitional inversion line on formulation–composition map. Such map in advance can certainly facilitate the guidelines for dynamic emulsification.     

Photophysical characteristics and density functional theory calculations of indole 2-carboxylic acid in the presence of mercurous ions

Many photo-physical studies have been reported for the detection of Hg²⁺ ions. Here we present the effect of Hg ₂ ²⁺ ions on the absorption and fluorescence of indole-2-carboxylic acid (I2C). Experimental evidence, supported by density functional theory B3LYP/LANL2DZ/PCM, for the formation of a I2C-Hg ₂ ²⁺ complex, is reported for the first time. It was observed that I2C forms a ground-state complex with Hg ₂ ²⁺ ions in a ratio of 3:1. The possibility of I2C to be used as a selective novel chemical sensor for the spectrophotometric detection of mercurous ions is described.     

Influence of crystallite size on acetone hydrogenation over copper catalysts

Acetone hydrogenation was studied over a family of Cu/SiO2 catalysts as well as UHP Cu powder and a Cu chromite catalyst. Oxygen chemisorption via dissociative N2O adsorption was used to count surface Cu atoms and calculate crystallite sizes, and a microwave absorption technique was used to measure the electrical conductivity of these Cu particles. Under differential reaction conditions at 423 K and 1 atm, all catalysts exhibited deactivation on stream and activities were typically 10-20% of their initial values after 3-4 h on stream. However, initial turnover frequencies (TOFs) varied from 0.056 s(-1) on the most highly dispersed Cu catalyst to 0.50 s(-1) on Cu powder, with the highest TOF of 2.4 s(-1) occurring on 110 nm crystallites. A similar trend with a broader (80-fold) variation was observed in the "steady-state" TOF values. Apparent activation energies varied between 11 and 14 kcal/mol. These initial TOF values are in good agreement with previous results, and a correlation exists between TOF and Cu crystallite size in this reaction, which appears to be structure sensitive. In addition, the electrical conductivity of these dispersed Cu nanoparticles, which was always less than that of bulk Cu, also increased with increasing Cu crystallite size; consequently, the change in this parameter may offer a possible explanation for the increase in TOF.