An Electrochemical Strategy to Synthesize Disilanes and Oligosilanes from Chlorosilanes**

Silanes are important compounds in industrial and synthetic chemistry. Here, we develop a general approach for the synthesis of disilanes as well as linear and cyclic oligosilanes via the reductive activation of readily available chlorosilanes. The efficient and selective generation of silyl anion intermediates, which are arduous to achieve by other means, allows for the synthesis of various novel oligosilanes by heterocoupling. In particular, this work presents a modular synthesis for a variety of functionalized cyclosilanes, which may give rise to materials with distinct properties from linear silanes but remain challenging synthetic targets. In comparison to the traditional Wurtz coupling, our method features milder conditions and improved chemoselectivity, broadening the functional groups that are compatible in oligosilane preparation. Computational studies support a mechanism whereby differential activation of sterically and electronically distinct chlorosilanes are achieved in an electrochemically driven radical-polar crossover mechanism.     

Propagation Rate Coefficients for Homogeneous Phase VDF–HFP Copolymerization in Supercritical CO2

For the first time, propagation rate coefficients, k_p,COPO, for the copolymerizations of vinylidene fluoride and hexafluoropropene have been determined. The kinetic data was determined via pulsed‐laser polymerization in conjunction with polymer analysis via size‐exclusion chromatography, the PLP‐SEC technique. The experiments were carried out in homogeneous phase with supercritical CO₂ as solvent for temperatures ranging from 45 to 90 °C. Absolute polymer molecular weights were calculated on the basis of experimentally determined Mark–Houwink constants. The Arrhenius parameters of k_p,COPO vary significantly compared with ethene, which is explained by the high electronegativity of fluorine and less intra‐ and intermolecular interactions between the partially fluorinated macroradicals.     

Room-temperature polariton lasing in semiconductor microcavities

We observe a room-temperature low-threshold transition to a coherent polariton state in bulk GaN microcavities in the strong-coupling regime. Nonresonant pulsed optical pumping produces rapid thermalization and yields a clear emission threshold of 1 mW, corresponding to an absorbed energy density of 29 microJ cm-2, 1 order of magnitude smaller than the best optically pumped (In,Ga)N quantum-well surface-emitting lasers (VCSELs). Angular and spectrally resolved luminescence show that the polariton emission is beamed in the normal direction with an angular width of +/-5 degrees and spatial size around 5 microm.     

Epitaxial growth of single-crystalline Al(2)O(3) films on Cr(2)O(3)(0001)

Thin, crystallographically oriented single-crystalline Al2O3 films can be grown epitaxially on Cr2O3(0001) by codeposition of Al vapor and O2 at a substrate temperature of 825 K. The properties and growth of these films were monitored by Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), low-energy ion scattering (LEIS), and X-ray photoelectron spectroscopy (XPS). Two routes of preparation were investigated: (i) stepwise growth by alternating deposition of Al at room temperature and subsequent exposure to O2 at elevated temperatures; (ii) codeposition of Al and O2 at T > 800 K. The first route was consistently found to result in the growth of a complex interfacial oxide followed by the growth of polycrystalline Al2O3. The second mode of preparation provided homogeneous and ordered, probably (0001)-oriented, films of Al2O3 that maintained a LEED pattern up to a thickness around 10 A. The surface sensitive Cr MVV Auger transition at 34 eV was completely attenuated once the Al2O3 layer had reached a thickness of 6 A, pointing to film homogeneity at an early stage. This was confirmed by the absence of a significant Cr signal in LEIS spectra.     

Preparation of 5-chloropyrazoles via tandem Meyer–Schuster/von Auwers rearrangements

A new, practical preparation of β,β-dichloroenones in three to four steps allows for a straightforward synthesis of 5-chloropyrazoles. Addition of various propargyl anions to commercially available 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one gives high yields of the corresponding propargyl alcohols. These are then transformed, in a single step, via two consecutive rearrangements, a Meyer–Schuster and a (sometimes spontaneous) von Auwers rearomatizing rearrangement, to deliver α,α-aryl-trichloromethylketones. After elimination of HCl, cyclization of the β,β-dichloroenones with various hydrazines delivers 5-chloropyrazoles. The four to five step sequence to 5-chloropyrazoles is very atom economical, expelling only water and two molecules of HCl from all the building blocks.     

Interaction of inert gases with a nickel (100) surface: I. Adsorption of xenon

The adsorption of Xe on a Ni(100) surface has been studied in UHV between 30 and 100 K using LEED, thermal desorption spectroscopy (TDS), work function (Δφ) measurements, and UV photoemission (UPS). At and below 80 K, Xe adsorbs readily with high initial sticking probability and via precursor state adsorption kinetics to form a partially ordered phase. This phase has a binding energy of ~5.2 kcal/mole as determined by isosteric heat measurements. The heat of adsorption is fairly constant up to medium coverages and then drops continuously as the coverage increases, indicating repulsive mutual interactions. The thermal desorption is first order with a preexponential factor of about 10¹² s^?1, indicative of completely mobile adsorption. Adsorbed Xe lowers the work function of the Ni surface by 376 mV at monolayer coverage. (This coverage is determined from LEED to be 5.65 × 10¹⁴ Xe molecules/cm^-2.) For not too high coverages, θ, Δφ(θ) can be described by the Topping model, with the initial dipole moment μ₀ = 0.29 D and the polarizability α being 3.5 × 10^?24 cm³. In photoemission, the $\text{Xe 5p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{5p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ orbitals show up as intense peaks at 5.56 and 6.83 eV below E_f which do not shift their position as the coverage varies. Multilayer adsorption (i.e. the filling of the second and third layers) can be seen by TDS. The binding energies of these α states can be estimated to range between 4.5 and 3.5 kcal/mole. The results are compared and contrasted with previous findings of Xe adsorption on other transition metal surfaces and are discussed with respect to the nature of the inert-gas-metal adsorptive bond.