Fluoride effect on the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates

Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd.     

Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins

A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru(VI)(TPP)(O)2] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru(II)(TPP)(S-DMSO)2] or [Ru(II)(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis.     

Complete thermodynamic analysis of the ionization of ortho-methoxybenzoic acid. Influence of the medium on the ortho effects

The ionization and solution enthalpies of o-methoxybenzoic acid have been measured in H₂O-DMSO mixtures. In the same solutions, the ΔG⁰ values for the ionization process have been determined by potentiometric measurements. A study of the ortho effects by means of a linear combination of the ordinary polar, proximity polar, and steric effects was also performed. The CH₃O group seems to undergo a partial steric inhibition of resonance. Finally, the proton transfer process from the ortho derivative to benzoic acid, compared with the same process in the gaseous phase, is presented.     

Thermodynamics of Dipeptides in Water. Influence of the hydrophobic forces of the side-chains on the dissociation processes for some series of dipeptides

A calorimetric study has been carried out on the dissociation processes in water of both the free α-amino group belonging to the amino terminal residue and the free α-carboxyl groups belonging to the carboxyl terminal residue for a series having phenylalanine as the first common term. These thermodynamic quantities have been compared with those of the proton dissociation processes related to the same groups of the corresponding singleα-amino acids. The dissociation process values of this series have also been considered in connection with those obtained from others series of dipeptides previously studied, in an effort to compare the alkyl groups and benzene ring hydrophobic effects on the salvation processes of the zwitterions, undissociated molecules and ionic forms. This revised version was published online in August 2006 with corrections to the Cover Date.     

Marine Sediments and Snow from Ross Sea Region (Antarctica) Dating by 210Pb Method

Abstract

²¹⁰Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of ²¹⁰Pb via its grand-daughter ²¹⁰Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of ²¹⁰Po from its matrix. In this work a simplified procedure for the chemical separation of ²¹⁰Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y^?1. The mean annual accumulation rate for the snow is 16.6 cm y^?1 w.e. A comparison with literature data in the same region is given.     

Boosting Conjugate Addition to Nitroolefins Using Lithium Tetraorganozincates: Synthetic Strategies and Structural Insights

We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R₄ZnLi₂) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R₄ZnLi₂ provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et₄ZnLi₂ into equimolar amounts of solvent-separated Et₃ZnLi and EtLi.     

Superior Antibacterial Activity of Integral Lemon Pectin Extracted via Hydrodynamic Cavitation

Pectin extracted via hydrodynamic cavitation in water only from waste lemon peel and further isolated via freeze drying displays significant antibacterial activity against Staphylococcus aureus, a Gram positive pathogen which easily contaminates food. The antibacterial effect of the new IntegroPectin is largely superior to that of commercial citrus pectin, opening the way to advanced applications of a new bioproduct now obtainable in large amounts and at low cost from citrus juice industry's waste.     

The evaporation–condensation problem for a binary mixture of rarefied gases

Continuum Mechanics and Thermodynamics - Half space problems of evaporation and condensation for a binary mixture of inert gases are investigated when the dynamics is governed by a system of...