A Convenient Large Scale Synthesis of 1, 1-Diphenyl-1 -silacyclopent-3-ene

An efficient one-step synthesis of 1,1-dipfienyl-1-silacyclopent-3-ene 1 is reported.     

Polymerization of Ethylene by Silica‐Supported Dinuclear CrIII Sites through an Initiation Step Involving C?H Bond Activation

The insertion of an olefin into a preformed metal–carbon bond is a common mechanism for transition‐metal‐catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal–carbon bond is not present in the precatalyst. The Phillips catalyst, CrO₃ dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first Cr C bond is formed remain unknown. We synthesized well‐defined dinuclear Cr^II and Cr^III sites on silica. Whereas the Cr^II material was a poor polymerization catalyst, the Cr^III material was active. Poisoning studies showed that about 65 % of the Cr^III sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si–(μ‐OH)–Cr^III species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at Cr^III O bonds.     

Characterization and kinetic performance of 2.1 × 100 mm production columns packed with new 1.6 μm superficially porous particles

The overall kinetic performance of three production columns (2.1 mm × 100 mm format) packed with 1.6 μm superficially porous CORTECS‐C₁₈+ particles was assessed on a low‐dispersive I‐class ACQUITY instrument. The values of their minimum intrinsic reduced plate heights (h_min = 1.42, 1.57, and 1.75) were measured at room temperature (295 K) for a small molecule (naphthalene) with an acetonitrile/water eluent mixture (75:25, v/v). These narrow‐bore columns provide an average intrinsic efficiency of 395 000 plates per meter. The gradient separation of 14 small molecules shows that these columns have a peak capacity about 25% larger than similar ones packed with fully porous BEH‐C₁₈ particles (1.7 μm) or shorter (50 mm) columns packed with smaller core–shell particles (1.3 μm) operated under very high pressure (>1000 bar) for steep gradient elution (analysis time 80 s). In contrast, because their permeabilities are lower than those of columns packed with larger core–shell particles, their peak capacities are 25% smaller than those of narrow‐bore columns packed with standard 2.7 μm core–shell particles.     

Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents

Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs.     

Synthesis,spectroscopic characterization (IR, 1H, 13C and 119Sn NMR,electrospray mass spectrometry) and toxicity of new organotin(IV) complexes with N,N′,O‐ and N,N′,S‐scorpionate ligands

New organotin(IV) derivatives containing the anionic ligands bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate [LCS₂]⁻ and bis(3,5‐dimethylpyrazol‐1‐yl)acetate [LCO₂]⁻ have been synthesized from reaction between (CH₃)₂SnCl₂ and lithium salts of the ligands. Mononuclear complexes of the type {[LCX₂](CH₃)₂SnCl} (X = S or O) have been obtained and fully characterized by elemental analyses and FT‐IR in the solid state and by NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry in solution. The acute toxicity of new organotin(IV) derivatives on rat was studied, comparing their effect with those of dimethyltin chloride (CH₃)₂SnCl₂. The comparison of LD₅₀ of organotin(IV) complexes and (CH₃)₂SnCl₂ administered intraperitoneally, as a single dose, evaluated in vivo on rats, showed that toxicity decreases as follows: (CH₃)₂SnCl₂ > LCO₂ > LCS₂. The effect of these organotin(IV) complexes on DNA was evaluated in vitro and in vivo on rats treated with different doses of these compounds (1/20 LD₅₀ and 1/100 LD₅₀). The lymphocyte DNA status was assessed by the comet assay, a rapid and sensitive single‐cell electrophoresis technique, used to detect primary DNA damage in individual cells. After 36 h from the start of treatment the two new organotin(IV) derivatives induced a significant rise in comet assay parameters, indicating an increasing presence of damaged DNA. Copyright © 2005 John Wiley & Sons, Ltd.     

Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations

Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]₂^2? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]₂^2? dimers form dissociated ion pairs with the NBu₄⁺ counterions, and their first solvation shell comprises approximately 20 CH₂Cl₂ molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE ^{. ?} in solution at 175 K is ?5.5 kcal mol^?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.     

High-fidelity front-end for high-power, high temporal quality few-cycle lasers

A 80???J, 6?fs, CEP-stable high-contrast injector is demonstrated. The device relies on standard pulse post-compression in hollow-core fiber followed by a temporal filter based on cross-polarized wave generation. Pulses with a Gaussian spectrum over 350?nm, centered at 750?nm, are generated. Temporal measurements show that the contrast of the few-cycle pulses is enhanced on a femtosecond and picosecond time scale. The carrier-envelope phase stability is preserved (0.3?rad RMS). These performances make the system an ideal seed laser for high-power, high-contrast OPCPA systems.     

Photoluminescence and optical absorption properties of silicon quantum dots embedded in Si-rich silicon nitride matrices

Silicon nitride (SiN_x) films were prepared with a gas mixture of SiH₄ and NH₃ on Si wafers using the plasma-enhanced chemical vapor deposition (PECVD) method. High-resolution transmission electron microscopy and infrared absorption have been used to reveal the existence of the Si quantum dots (Si QDs) and to determine the chemical composition of the silicon nitride layers. The optical properties of these structures were studied by photoluminescence (PL) spectroscopy and indicate that emission mechanisms are dominated by confined excitons within Si QDs. The peak position of PL could be controlled in the wavelength range from 1.5 to 2.2 eV by adjusting the flow rates of ammonia and silane gases. Absorbance spectra obtained in the transmission mode reveal optical absorption from Si QDs, which is in good correlation with PL properties. These results have implications for future nanomaterial deposition controlling and device applications.