Vanadium(V) oxo and imido calix[8]arene complexes: synthesis, structural studies, and ethylene homo/copolymerisation capability

Interaction of p-tert-butylcalix[8]areneH₈ (L⁸H₈) with in-situ generated [NaVO(Ot-Bu)₄] (from VOCl₃ and four equivalents of NaOtBu) afforded the dark brown complex [Na(NCMe)₅][(VO)₂L⁸H]·4MeCN (1·4MeCN), in which the calix[8]arene adopts a saddle-shaped conformation. Increasing (to four equivalents per L⁸) the amount of [NaVO(Ot-Bu)₄] present in the reaction, led to the formation of the yellow octa-vanadyl complex {[(Na(VO)₄L⁸)(Na(NCMe))₃] [Na(NCMe)₆}₂·10MeCN (2·10MeCN), in which the calix[8]arene adopts a pleated loop conformation. In the presence of adventitious oxygen, reaction of four equivalents of [VO(Ot-Bu)₃] (generated from VOCl₃ and 3KOtBu) with L⁸H₈ afforded the alkali-metal free green complex [(VO)₄L⁸(μ³-O)₂] (3); the solvates 3·3MeCN and 3·3CH₂Cl₂ have been isolated. In both solvates, the L⁸ ligand adopts a shallow saddle-shaped conformation, supporting a core comprising of a (VO)₄O₄ ladder. In the case of lithium, in order to obtain crystalline material, it was found necessary to reverse the order of addition such that lithium tert-butoxide was added to L⁸H₈, and then subsequently treated (at –78 ⁰C) with two equivalents of VOCl₃; crystallization from tetrahydrofuran (THF) afforded {(VO₂)₂Li₆[L⁸](thf)₂(OtBu)₂(Et₂O)₂}·Et₂O (4·Et₂O). In the structure of 4·Et₂O, vanadium, lithium and oxygen form a central lattern-type cage, which is capped top and bottom by an Li₂O₂2 diamond; the calix[8]arene is in a ‘down, down, out, out, down, down’ conformation. When the ‘same reaction’ was extracted into acetonitrile (MeCN), the salt complex [Li(NCMe)₄][(VO)₂L⁸H]·8MeCN (5.8MeCN) was formed. In 5·8MeCN, the [Li(NCMe)₄] cations reside between the anions in the clefts of L⁸H, the latter adopting a saddle-shaped conformation. Use of the imido precursors [V(Nt-Bu)(Ot-Bu)₃] and [V(Np-tolyl)(Ot-Bu)₃] and L⁸H₈, afforded, via an imido exchange, the salt [t-BuNH₃]{[V(p-tolylN)]₂L⁸H}·3½MeCN (6·3½MeCN). The molecular structures of 1 to 6 are reported; data collections for complexes 2·10MeCN, 3·3MeCN and 3·3CH₂Cl₂ required the use of synchrotron radiation. Complexes 1, 3 and 4 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst VO(OEt)Cl₂. In some cases, activities as high as 136,000 g/mmol.v.h were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparible yields) versus the use of VO(OEt)Cl₂. In the case of the co-polymerization, the incorporation of propylene was 7.1 – 10.9 mol% (cf 10 mol% for VO(OEt)Cl₂), though catalytic activities were lower versus VO(OEt)Cl₂

Invasion of winter moth in New England: Effects of defoliation and site quality on tree mortality.

Abstract Widespread and prolonged defoliation by the European winter moth, Operophtera brumata L., has occurred in forests of eastern Massachusetts for more than a decade and populations of winter moth continue to invade new areas of New England. This study characterized the forests of eastern Massachusetts invaded by winter moth and related the duration of winter moth defoliation estimated using dendrochronology to observed levels of tree mortality and understory woody plant density. Quercus basal area mortality in mixed Quercus and mixed Quercus-Pinus strobus forests in eastern Massachusetts ranged from 0-30%; mortality of Quercus in these forests was related to site quality and the number of winter moth defoliation events. In addition, winter moth defoliation events lead to a subsequent increase in understory woody plant density. Our results indicate that winter moth defoliation has been an important disturbance in New England forests that may have lasting impacts

Signatures of unconventional pairing in near-vortex electronic structure of LiFeAs

A major question in Fe-based superconductors remains the structure of the pairing, in particular whether it is of unconventional nature. The electronic structure near vortices can serve as a platform for phase-sensitive measurements to answer this question. By solving Bogoliubov-de Gennes equations for LiFeAs, we calculate the energy-dependent local electronic structure near a vortex for different nodeless gap-structure possibilities. At low energies, the local density of states (LDOS) around a vortex is determined by the normal-state electronic structure. However, at energies closer to the gap value, the LDOS can distinguish an anisotropic from a conventional isotropic s-wave gap. We show within our self-consistent calculation that in addition, the local gap profile differs between a conventional and an unconventional pairing. We explain this through admixing of a secondary order parameter within Ginzburg-Landau theory. In-field scanning tunneling spectroscopy near vortices can therefore be used as a real-space probe of the gap structure

Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO₂, ZnO, γ-Al2O₃, CeO₂ is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO₂ and γ-Al₂O₃. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature

They Were Meant for Each Other: Professor Edward Cooper and the Rules Enabling Act

This introduction to the essays in this Symposium illuminates Professor Ed Cooper\u27s years as Reporter to the Civil Rules Committee by first briefly describing those who preceded him in the position and his own background. We then describe some of Ed Cooper\u27s many contributions to the Civil Rules Committee, the Federal Rules, rulemaking, and civil procedure by examining the present state of the Rules Committees\u27 work under the Rules Enabling Act. We conclude that after almost eighty years of experience under that Act, it is working well in large part because of the sound leadership provided by Ed Cooper over his twenty years as Reporter. It was during these years that the Committee developed an approach to rulemaking that was at once transparent and empirical, with multiple opportunities for participation by members of the public, the bench, the academy, and the bar; with many informal opportunities for consultation with members of Congress and the Executive Branch; and with an understanding by the Committee of its role in relation to the courts, Congress, and the Executive. Two episodes of recent rulemaking and related activity are described as examples of how well the Rules Enabling Act is working, in large part because of the very flexibility and discretion the Act has provided since 1934. One of those episodes occurred when Judge Anthony Scirica chaired the Standing Committee and then- Judge David Levi chaired the Civil Rules Committee. The other occurred when Judge Lee Rosenthal and Judge Mark Kravitz were the chairs of the Standing and Civil Rules Committees, respectively. Both episodes provide a basis for optimism about the future. And they make clear Ed Cooper\u27s continued steady role in supporting and cultivating the robust good health of the rulemaking process and the institutional values it protects

Efficient Universal Noiseless Source Codes

Although the existence of universal noiseless variable-rate codes for the class of discrete stationary ergodic sources has previously been established, very few practical universal encoding methods are available. Efficient implementable universal source coding techniques are discussed in this paper. Results are presented on source codes for which a small value of the maximum redundancy is achieved with a relatively short block length. A constructive proof of the existence of universal noiseless codes for discrete stationary sources is first presented. The proof is shown to provide a method for obtaining efficient universal noiseless variable-rate codes for various classes of sources. For memoryless sources, upper and lower bounds are obtained for the minimax redundancy as a function of the block length of the code. Several techniques for constructing universal noiseless source codes for memoryless sources are presented and their redundancies are compared with the bounds. Consideration is given to possible applications to data compression for certain nonstationary sources

Trispectrum versus Bispectrum in Single-Field Inflation

In the standard slow-roll inflationary cosmology, quantum fluctuations in a single field, the inflaton, generate approximately Gaussian primordial density perturbations. At present, the bispectrum and trispectrum of the density perturbations have not been observed and the probability distribution for these perturbations is consistent with Gaussianity. However, Planck satellite data will bring a new level of precision to bear on this issue, and it is possible that evidence for non-Gaussian effects in the primordial distribution will be discovered. One possibility is that a trispectrum will be observed without evidence for a non-zero bispectrum. It is not difficult for this to occur in inflationary models where quantum fluctuations in a field other than the inflaton contribute to the density perturbations. A natural question to ask is whether such an observation would rule out the standard scenarios. We explore this issue and find that it is possible to construct single-field models in which inflaton-generated primordial density perturbations have an observable trispectrum, but a bispectrum that is too small to be observed by the Planck satellite. However, an awkward fine tuning seems to be unavoidable.Comment: 15 pages, 3 figures; journal versio