Photopolymerization of 1,6‐hexanedioldiacrylate initiated by three‐component systems based on N‐arylphthalimides

Three‐component photoinitiators comprised of an N‐arylphthalimide, a diarylketone, and a tertiary amine were investigated for their initiation efficiency of acrylate polymerization. The use of an electron‐deficient N‐arylphthalimide resulted in a greater acrylate polymerization rate than an electron‐rich N‐arylphthalimide. Triplet energies of each N‐arylphthalimide, determined from their phosphorescence spectra, and the respective rate constants for triplet quenching by the N‐arylphthalimide derivatives (acquired via laser flash photolysis) indicated that an electron–proton transfer from an intermediate radical species to the N‐arylphthalimide (not energy transfer from triplet sensitization) is responsible for generating the initiating radicals under the conditions and species concentrations used for polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4009–4015, 2004     

The thermolysis of dicarbonylcyclopentadienyliron dimer: The formation of biferrocene

The thermolysis of dicarbonylcyclopentadienyliron dimer in a sealed tube at 300°C has been reported to produce ferrocene, carbon monoxide, carbon dioxide, cyclopentadiene and elemental iron. We observe in addition to these products the production of biferrocene and elemental carbon. Thermolysis of carbonylcyclopentadienyliron tetramer (produced from the dimer by thermolysis in refluxing xylene) produces ferrocene, iron and carbon monoxidre; no biferrocene, carbon dioxide or elemental carbon are produced. A scheme is proposed to account for these products.     

Effect of nanotube functionalization on the properties of single‐walled carbon nanotube/polyurethane composites

A commercially available aliphatic thermoplastic polyurethane formulated with a methylene bis(cyclohexyl) diisocyanate hard segment and a poly(tetramethylene oxide) soft segment and chain‐extended with 1,4‐butanediol was dissolved in dimethylformamide and mixed with dispersed single‐walled carbon nanotubes. The properties of composites made with unfunctionalized nanotubes were compared with the properties of composites made with nanotubes functionalized to contain hydroxyl groups. Functionalization almost eliminated the conductivity of the tubes according to the conductivity of the composites above the percolation threshold. In most cases, functionalized and unfunctionalized tubes yielded composites with statistically identical mechanical properties. However, composites made with functionalized tubes did have a slightly higher modulus in the rubbery plateau region at higher nanotube fractions. Small‐angle X‐ray scattering patterns indicated that the dispersion reached a plateau in the unfunctionalized composites that was consistent with the plateau in the rubbery plateau region. The room‐temperature modulus and tensile strength increase was proportionally higher than almost all increases seen previously in thermoplastic polyurethanes; however, the increase was still an order of magnitude below what has been reported for the best nanotube–polymer systems. Nanotube addition increased the hard‐segment glass transition temperature slightly, whereas the soft‐segment glass transition was so diffuse that no conclusions could be drawn. Unfunctionalized tubes suppressed the crystallization of the hard segment; whereas functionalized tubes had no effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 490–501, 2007     

Reconstruction of an acoustically sound-soft obstacle from one incident field and the far-field pattern

The problem considered is that of determining the shape of aplane acoustically sound-soft obstacle from the knowledge ofthe far-field pattern for one time-harmonic incident field.An iterative procedure is proposed based on two boundary integralsrepresenting the incident field and the far-field pattern, respectively.Numerical examples are included which show that the proceduregives accurate numerical approximations in relatively few iterations.     

Photochemical reactions of Ru3(CO)12 involving metalmetal bond fission

Photolysis of Ru₃(CO)₁₂ in the presence of donor ligands rapidly produces monomeric ruthenium species.     

Metal to ligand group transfer reactions : II. Reactions of some π-allylrhodium(I) complexes with trifluoroacetic acid and alkyl,acyl and trimethyltin halides

Rh(π-C₃H₅)(PF₃)₃ (I), reacts with trifluoroacetic acid to form propene and [Rh(CF₃COO)(PF₃)₂]₂ (II). I reacts with t-butyl bromide to give [RhBr(PF₃)₂]₂ and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF₃)₂]₂. Rh(π-C₃H₅)(PPh₃)₂ (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me₃SnCl the Me₃Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF₃)₂]₂ and the carbonyl rhodium complex Rh₂Cl₂(PF₃)₃(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers.     

High-resolution spectroscopy of induced chiral dimers: a study of the dimers of ethanol by Fourier transform microwave spectroscopy

We present the first recording of the high-resolution spectrum of an induced chiral dimer. Three conformers of the induced chiral dimers of ethanol have been observed using a pulsed molecular-beam Fourier transform microwave spectrometer. The rotational constants of the normal isotopomers of the three species have been determined to be (a) A=5113.826(5), B=1329.7214(4), and C=1257.5151(3) MHz, (b) A=5086.459(5), B=1316.6508(4), and C=1243.6329(4) MHz, and (c) A=4851.608(5), B=1369.7558(6), and C=1243.4184(4) MHz. The observed species have been assigned to calculated structures via Kraitchman double substitution analyses and ab initio calculations. The Kraitchman analyses and the fitted centrifugal distortion parameters suggest that the deuterium bond is significantly stronger than the hydrogen bond in the dimers of ethanol.     

Consistent propagator approximations

A propagator approximation scheme is presented in the context of an abstract*-algebra approach. The representation theory of such algebras is shown to play a crucial role in the definition of consistent approximations, i.e., approximate propagators based on model time evolutions and states. This procedure places superoperator methods of approximation on a sound Hilbert space footing. A generalization of the Fock vacuum property is introduced which leads to a simplification in the form of the model propagators. Finally a concrete example is considered that fulfills the conditions developed in this article showing that a consistent approximation to the electron propagator results in the Hartree–Fock–Boguliubov equations.