Preparation,characterization and a kinetic study oftrans-[Ru(NH3)4L(H2O)](PF6)2 [L=PPh3, AsPh3, or SbPh3]

Summary The complexestrans-[Ru(NH₃)₄(H₂O)PPh₃](PF₆)₂ and [Ru(NH₃)₅L](PF₆)₂, (L=AsPh₃ or SbPh₃) have been isolated and characterized by microanalysis, cyclic voltammetry and ultraviolet-visible spectroscopy. The specific rate constants for the aquation of [Ru(NH₃)₅L]²⁺ totrans-[Ru(NH₃)₄L(H₂O)]²⁺ are (2.5±0.1)×10^–5s^–1 and (1.8±0.1)×10^–5s^–1 for L=AsPh₃ and SbPh₃, respectively, at 25.0±0.1°C; =0.10 mol dm^–3, NaO₂CCF₃. Under the same conditions, the second-order rate constants for the substitution of water intrans-[Ru(NH₃)₄(H₂O)L]²⁺ by isonicotinamide (isn) are 1.2±0.1, (6.3±0.3)×10^–2 and (3.8±0.2)×10^–2 m ^–1s^–1 for L=PPh₃, AsPh₃, and SbPh₃, respectively, suggesting that the order of decreasingtrans-effect is: PPh₃AsPh₃>SbPh₃. The formation constants for thetrans-[Ru(NH₃)₄L(isn)]²⁺ complexes are 75±3, (1.40±0.01)×10³ and (1.80±0.02)×10³M^–1 for L=PPh₃, AsPh₃, and SbPh₃, respectively, suggesting that the order of increasingtrans-influence is: SbPh₃3PPh₃.     

BIOLOGICAL ACTIVITIES OF PHTHALOCYANINES-X. SYNTHESES AND ANALYSES OF SULFONATED PHTHALOCYANINES

Abstract— Synthetic methods to obtain selectively sulfonated metallo phthalocyanines are compared. Both condensation and direct sulfonation procedures lead to mixtures of mono- to tetrasulfonated products which are resolved by reverse phase liquid chromatography in buffered aqueous-methanol. The proportion of sulfonated derivatives is examined as a function of the starting reagents in the case of the condensation method, and as a function of the temperature and reaction time in the case of the direct sulfonation procedure. The number of sulfonate groups per phthalocyanine molecule is determined by oxidative degradation of the phthalocyanine ring followed by quantitative chromatographic analysis of the sulfophthalamide and phthalamide fragments.     

A straightforward preparation of amino–polystyrene resin from Merrifield resin

Azidomethyl–polystyrene, obtained by nucleophilic substitution of chloromethyl–polystyrene, undergoes a Schmidt rearrangement when treated with trifluoromethanesulfonic acid, affording amino–polystyrene. To assess its loading and reactivity the resin is used as a support for the preparation of triazene-linked amine.     

Application of preparative high-speed counter-current chromatography for the separation of flavonoids from the leaves of Byrsonima crassa Niedenzu (IK)

The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses.     

Photolysis of hexamethyldisilane at 206 nm

The photolysis of Me₆Si₂ at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me₃SiH elimination with the concomitant formation of Me₂SiCH₂ with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10⁻³, which results in the formation of Me₄Si and Me₂Si. The main fate of the excited Me₆Si₂ molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me₃Si and Me₂SiCH₂, are the same as those found in the photolysis of Me₄Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33).     

Beryllium diffusion across GaAs/(Al,Ga)As heterojunctions and GaAs/AlAs superlattices during MBE growth

Beryllium diffusion during MBE growth of (Al, Ga)As layers, (Al, Ga)As/GaAs heterojunctions and GaAs/AlAs superlattices has been studied by electrochemical C-V and secondary ion mass spectrometry (SIMS) concentration profiling, in conjunction with transmission electron microscopy. Diffusion times were comparatively short since they were limited to part of the growth sequence, so non-equilibrium effects had a significant influence. The results are consistent with an interstitial-substitutional mechanism in which lattice site incorporation becomes more difficult with increasing band gap enthalpy. Incorporation involves a kick-out reaction which leads to the observed disordering of the superlattices.     

Photopyroelectric spectroscopy (P2ES) of electronic defect centers in crystalline n-CdS

The electrical and dielectric properties of mercuric iodide were studied at room temperature under various intensities and colours of light in the frequency range 1 Hz–10 kHz. In the high-frequency region (>40 Hz), the real part of the dielectric constant () is almost constant with frequency (f), colour and intensity of light. At lower frequencies, varies nearly as 1/f and monotonically increases with intensity (I) of the yellow (or green) light, whereas it is almost constant with red light intensity. This behaviour is discussed in the view of the different polarization contributions. The imaginary part of the dielectric constant () was found to vary as 1/f over the frequency range studied. This behaviour was observed whether the crystal was in dark or illuminated implying that the roomtemperature ac dark- or photo-conductivity () is independent of frequency. The observed variation of with intensity of yellow (or green) light was found to follow anI ^1/2 dependence and a weaker dependence for the red light. the red light. The conductivity behaviour is discussed in the view of the current theories.