Reaction of bis(phosphine)(hydrotris(3,5-dimethylpyrazolyl)borato)rhodium(I) with phenylacetylene,p-nitrobenzaldehyde,and triphenyltin hydride: structures of [Rh(Tp)(PPh(3))(2)], [Rh(Tp)(H)(C(2)Ph)(P(4-C(6)H(4)F)(3))], [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PPh(3))], and [Rh(Tp)(H)(SnPh(3))(PPh(3))

The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported.     

Liquid Chromatography-Electrospray Mass Spectrometry Determination of Ibogaine and 12-Hydroxy-Ibogamine in Human Urine

A specific and sensitive liquid chromatography-electrospray ionization mass spectrometry method was developed for the determination of ibogaine and noribogaine in human urine. The work-up procedure involved a solid phase extraction of the compounds and the internal standard (fluorescein) using Oasis HLB columns. The system used a Zorbax eclipse XDB C8 analytical column packed with 5µm diameter particles as the stationary phase. The mobile phase consisted of a 20-min gradient (mobile phase A: 0.02% (v/v) trimethylamine in acetonitrile, mobile phase B: 2 mM ammonium formate buffer (pH 3)). Mass spectrometric data were acquired in single ion monitoring mode at m/z 311.1, 297.2 and 333 for ibogaine, noribogaine and fluorescein, respectively. The drug/internal standard peak area ratios were linked via a quadratic relationship to concentrations (1.78?358 μg L^?1 for ibogaine; 2?400 μg L^?1 for noribogaine). Precision ranged from 5.8 to 14.8% and accuracy was between 93.2 and 112.9%. Mean extraction recoveries of ibogaine, noribogaine and fluorescein were 70.0, 81.7 and 94.8%, respectively. The extraction efficiency was independent of concentration over the range studied. The lower limits of quantitation were 1.78 μg L^?1 for ibogaine and 2 μg L^?1 for noribogaine. In this paper, extensive stability testing was undertaken using a wide range of storage conditions. This method was found suitable for urine analysis of a poisoning involving ingestion of drink made from powdered root of shrub Tabernanthe iboga.     

Rhodium(I) complexes with 1′-(diphenylphosphino)ferrocenecarboxylic acid as active and recyclable catalysts for 1-hexene hydroformylation

The rhodium complex trans-[Rh(CO)(Hdpf-κP)(dpf-κ²O,P)] (1), (Hdpf = 1′-(diphenylphosphino)ferrocenecarboxylic acid) was used as an efficient and recyclable catalyst for 1-hexene hydroformylation producing ca. 80% of aldehydes at 10 atm CO/H₂ and 80 °C. After the reaction, unchanged complex 1 was separated from the reaction mixture and used again three times with the same catalytic activity. The effect of modifying ligands, phosphines and phosphites, on the reactivity of 1 was investigated. The active catalytic systems containing 1 or trans-[Rh(CO)(L)(dpf-κ²O,P)] (2) were formed in situ from acetylacetonato rhodium(I) precursors [Rh(CO)₂(acac)] (3) or [RhL(CO)(acac)] (4) and Hdpf or Medpf (L = phosphine, Medpf = methyl ester of Hdpf).     

Surface patterns of block copolymers in thin layers after vapor treatment

A systematic study of formation of surface patterns in block copolymer thin layers after their exposure to solvent vapors was performed. The studied effect involves layers of thickness approximately equal to the ordering size of polymers - about 45 nm. Experiments were performed on three styrene - methacrylate derivative block copolymers, synthesized by living anionic polymerization: poly(4-octylstyrene)-block-poly(butyl methacrylate), poly(4-fluorostyrene)-block-poly(butyl methacrylate) and poly(p-octylstyrene)-block-poly(methyl methacrylate). The polymers were exposed to vapors of chloroform, 1,4-dioxane, hexane, acetone and tetrahydrofuran.     

Efficient synthesis of trisubstituted alkenes in an aqueous-organic system using a versatile and recyclable Rh/m-TPPTC catalyst

We have found that the use of [Rh(cod)OH]₂ associated with the water-soluble ligand m-TPPTC was highly efficient for the Rh-catalyzed arylation of alkynes. Aryl and alkyl alkynes were transformed to alkenes using 3 mol % rhodium catalyst and 2.5 equiv of boronic acid at 100 °C in a biphasic water/toluene system in 80-99% yield. The reaction was found to be totally regioselective for alkyl arylalkynes and alkyl silylated alkynes. The Rh/m-TPPTC system was for the first time recycled with no loss of the activity and with excellent purity of the desired alkene.     

Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry

A series of arene-ruthenium complexes of the general formula [RuCl₂{η⁶-C₆H₅(CH₂)₂R}L] with R=OH, CH₂OH, OC(O)Fc, CH₂OC(O)Fc (Fc=ferrocenyl) and L=PPh₃, (diphenylphosphino)ferrocene, or bridging 1,1^′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl₃ · nH₂O to afford [RuCl₂{η⁶-C₆H₅(CH₂)₂OC(O)Fc}]₂, and (b) esterification between ferrocene carboxylic acid and [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}L] to give [RuCl₂{η⁶-C₆H₅(CH₂)₃OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}(PPh₃)] shows that the presence of a CH₂CH₂CH₂OH side-arm allows [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}(PPh₃)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.     

Particle size determination of platinum, palladium and rhodium

Simple and sufficiently accurate equations are suggested for calculating the particle size of most frequently used supported or unsupported platinum metal catalysts from the amount of chemisorbed gas.

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Retaining60Co2+ ions from residual water on zeolites

The ion exchange between⁶⁰Co²⁺ ions contained in residual radioactive water and zeolites of the NaA, NaX and CaA types was studied. The more advanced retaining of⁶⁰Co²⁺ ions occurs for the NaA zeolite with the higher exchange capacity, as compared to NaX. With the CaA zeolite, a very weak ion exchange with⁶⁰Co²⁺ ions was observed.     

Molecular dynamics study of hydration in ethanol-water mixtures using a polarizable force field

The abnormal physicochemical characteristics of ethanol solvation in water are commonly attributed to the phenomenon of hydrophobic hydration. To investigate the structural organization of hydrophobic hydration in water-ethanol mixtures, we use molecular dynamics simulations based on detailed atomic models. Induced polarization is incorporated into the potential function on the basis of the classical Drude oscillator model. Water-ethanol mixtures are simulated at 11 ethanol molar fractions, from 0.05 to 0.9. Although the water and ethanol models are parametrized separately to reproduce the vaporization enthalpy, static dielectric constant, and self-diffusion constant of neat liquids at ambient conditions, they also reproduce the energetic and dynamical properties of the mixtures accurately. Furthermore, the calculated dielectric constant for the various water-alcohol mixtures is in excellent agreement with experimental data. The simulations provide a detailed structural characterization of the mixtures. A depletion of water-water hydrogen bonding in the first hydration shell of ethanol is compensated by an enhancement in the second hydration shell. The structuring effect from the second solvation shell gives rise to a net positive hydrogen-bonding excess for ethanol molar fractions up to approximately 0.5. For larger molar fractions, the second hydration shell is not sufficiently populated to overcome the net H-bond depletion from the first shell.     

Determination of acid sites on carbon surface

Pyridine chemisorbed on acid sites of active carbon was displaced by n-butylamine and the displaced amount was measured spectrophotometrically. This amount, supposed to be proportional to the surface concentration of carboxy groups, depends on the chemical pretreatment of active carbon.

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