Synthesis, isolation, and characterization of an organometallic triiodopalladium(IV) complex. Quantitative and regioselective synthesis of two C-I reductive elimination products

Iodine and the pincer complex [Pd(O,N,C-L)I], where L is the monoanionic ligand resulting from deprotonation of the acetyl group of the dimethylmonoketal of 2,6-diacetylpyridine, are in equilibrium at low temperatures with the palladium(IV) complex [Pd(O,N,C-L)I(3)], which can be isolated at -40 °C and characterized by (1)H NMR spectroscopy and X-ray diffraction studies, in spite of its great instability. When the same reaction is carried out at room temperature, a quantitative reductive elimination process occurs, giving L-I, which in the presence of water affords L'-I, resulting from hydrolysis of L-I.     

Synthesis and Molecular Structure of β‐Phosphinoyl Carboxamides: An Unexpected Case of Chiral Discrimination of Hydrogen‐Bonded Dimers in the Solid State

A series of N,P,P‐trisubstituted aminophosphanes react with diphenylcyclopropenone to afford an easily separable mixture of two diastereomeric α,β‐diphenyl‐β‐phosphinoyl carboxamides in good yields. X‐ray crystal structures reveal that these compounds associate into dimers, formed from two enantiomeric units linked by two bifurcated hydrogen bonds, whereby the oxygen atom of the phosphoryl group acts as a dual acceptor for the vicinal NH and CH of a carbonyl group of a neighbouring molecule. Studies on the interconversion between diastereomeric phosphinoyl carboxamides in basic solution show that the thermodynamically most stable isomer depends on the nature of the substituent at the nitrogen atom. Simple computational calculations explain this phenomenon.     

Advances and analytical applications in chemiluminescence coupled to capillary electrophoresis

The present review presents the state of the art of the developments, key strategies and analytical applications of chemiluminescence detection coupled to CE (CE‐CL). Different parts considering the most common CL systems have been included, such as the tris(2,2′‐bipyridine)ruthenium(II) system, the luminol and derivatives reaction, the peroxyoxalate CL or direct oxidations. New advances in homemade configurations and applications in different fields such as clinical, pharmaceutical, environmental and food analysis have been included. The focus is on studies which appeared from 2000 to the end of 2009.     

Pulsed gradient spin echo (PGSE) diffusion measurements as a tool for the elucidation of a new type of hydrogen-bonded bicapsular aggregate

Compounds formed by linking two tris(ureidobenzyl)amine modules with a hexamethylene tether are described. These compounds self-assemble to form bicapsular aggregates featuring two rings of six hydrogen-bonded ureas. (1)H and (1)H/(1)H ROESY NMR spectroscopy, together with pulsed gradient spin echo (PGSE) NMR diffusion measurements, have been used to characterize the dimers in solution. The results have been compared with energy-minimized structures. The new compounds are kinetically stable on the NMR timescale, and their thermodynamic stabilities are comparable to other capsular aggregates derived from tris(ureidobenzyl)amines.     

Template polymerization of methacrylic acid along poly(N-acetyliminoethylene) in water. Influence of template architecture

The kinetic study of the photochemical polymerization of methacrylic acid (MAA) in aqueous dilute solution in the presence of poly(N-acetyliminoethylene) (PNAI) oligomers evidenced template features. The process proceeded in two stages, depending on [PNAI]/[MAA]₀ ratio and polymerization duration, two different complexes being formed, both by a “zip” chain-growth mechanism. Computing and transmission electron microscopy data revealed that this aspect is due to the replacing of the initial PNAI template by the newly formed poly(methacrylic acid) daughter polymer, as a result of the structural peculiarities of the latter as a component of the primary complex. Its specific mode of packing in a complex aggregate was considered to be the main reason for the reported behavior. © 1996 John Wiley & Sons, Inc.     

Drop deformation under surfactants adsorption

The movements of free liquid drops, resulting from unbalanced surface tension gradients, in our case the adsorption of a surfactant, constitute important surface phenomena (Marangoni effect). The aim of this paper is to correlate the effect of pressure forces on the drop, with the surface coverage degree, namely with the extent to which the drop surface is covered by the surfactant. Our model shows that for a covered degree less then about 68°, these forces are negative. This means that these forces exerted by the external liquid upon the drop are oriented towards the negative direction of the normal to the drop surface, acting like a hammer. Some numerical data are given. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

SiO2-Iron Oxide Composites Obtained by Sol-Gel Method

Composite SiO₂-iron oxide materials were prepared by three experimental procedures. In the first case (1), the iron oxides were precipitated during the sol-gel process. In the second case (2), the SiO₂ matrix was initially obtained, and the iron oxides were formed by thermal treatment after impregnation of a soluble Fe²⁺ salt in the previously processed matrix. In the third method (3), ferrite powders, prepared by wet chemical method, were embedded into a SiO₂ based sol-gel matrix. Two type of precursors (tetraethoxysilane (TEOS) or methyltriethoxysilane (MTEOS) were used as SiO₂ sources. Various properties versus both type of precursor and on the method of preparation were noticed. Materials with high porosity and nano-sized iron oxide content could be prepared using the mentioned above methods.     

The Study of Zeolite ZSM-5 by Auger Electron Spectroscopy

The dependence of the surface Si/Al ratio in function of the volume Si/Al ratio was studied, for zeolite of type: A, X, clinoptilolite, mordenite and three samples of ZSM-5. Surface measurements were made by Auger electron spectroscopy (AES), and volume (bulk) measurements by atomic absorption spectrophotometry. It was found that the surface Si/Al ratio is identical with the volume Si/Al ratio. The dependence of the surface Si/Al ratio on the crystallization degree for zeolite ZSM-5 was also studied. We obtained some informations about the kinetics and mechanism of the crystallization process.