Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis

The alkylaluminum-complexed zirconocene trihydride cation [(SBI)Zr(μ-H)_3(AliBu_2)_2]^+, which is obtained by reaction of (SBI)ZrCl_2 with [Ph_3C][B(C_6F_5)_4] and excess HAl^iBu_2 in toluene solution, catalyzes the formation of isotactic polypropene when exposed to propene at -30 °C. This cation remains the sole observable species in catalyst systems free of AlMe compounds. In the presence of AlMe_3, however, exposure to propene causes the trihydride cation to be completely converted, under concurrent consumption of all hydride species by propene hydroalumination, to the doubly Me-bridged cation [(SBI)Zr(μ-Me)_2AlMe_2]^+. The latter then becomes the resting state for further propene polymerization, which produces, by chain transfer to Al, mainly AlMe_2-capped isotactic polypropene

Alkylaluminum-complexed zirconocene hydrides: identification of hydride-bridged species by NMR spectroscopy

Reactions of unbridged zirconocene dichlorides, (R_nC_5H_5−n)_2ZrCl_2 (n = 0, 1, or 2), with diisobutylaluminum hydride (HAl^iBu_2) result in the formation of tetranuclear trihydride clusters of the type (R_nC_5H_5−n)_2Zr(μ-H)_3(Al^iBu_2)_3(μ-Cl)_2, which contain three [Al^iBu_2] units. Ring-bridged ansa-zirconocene dichlorides, Me_2E(R_nC_5H_4−n)_2ZrCl_2 with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me_2E(R_nC_5H_4−n)_2Zr(Cl)(μ-H)_2Al^iBu_2 with only one [Al^iBu_2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C_5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAl^iBu_2 or Al^iBu_3, are proposed to be species of the type Me_2Si(ind)_2Zr(Me)(μ-H)_2Al^iBu_2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO

Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations

The ansa-zirconocene complex rac-Me_2Si(1-indenyl)_2ZrCl_2 ((SBI)ZrCl_2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)_3(Al^iBu_2)_2]^+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)_3(Al^iBu2)_2]^+ reacts reversibly with ClAl^iBu_2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)_2Al^iBu_2]^+. Reaction with AlMe_3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)_3(AlMe_x^iBu_(2−x))_2^]+ by exchange of alkyl groups between aluminum centers. At higher AlMe_3/Zr ratios, [(SBI)Zr(μ-Me)_2AlMe_2]^+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)_3(AlR_2)_2]^+ strongly predominates at comparable HAl^iBu_2 and AlMe_3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems

A review of modular strategies and architecture within manufacturing operations

This paper reviews existing modularity and modularization literature within manufacturing operations. Its purpose is to examine the tools, techniques, and concepts relating to modular production, to draw together key issues currently dominating the literature, to assess managerial implications associated with the emerging modular paradigm, and to present an agenda for future research directions. The review is based on journal papers included in the ABI/Inform electronic database and other noteworthy research published as part of significant research programmes. The research methodology concerns reviewing existing literature to identify key modular concepts, to determine modular developments, and to present a review of significant contributions to the field. The findings indicate that the modular paradigm is being adopted in a number of manufacturing organizations. As a result a range of conceptual tools, techniques, and frameworks has emerged and the field of modular enquiry is in the process of codifying the modular lexicon and developing appropriate modular strategies commensurate with the needs of manufacturers. Modular strategies and modular architecture were identified as two key issues currently dominating the modular landscape. Based on this review, the present authors suggest that future research areas need to focus on the development and subsequent standardization of interface protocols, cross-brand module use, supply chain power, transparency, and trust. This is the first review of the modular landscape and as such provides insights into, first, the development of modularization and, second, issues relating to designing modular products and modular supply chains

Spectrophotometry of 2 complete samples of flat radio spectrum quasars

Spectrophotometry of two complete samples of flat-spectrum radio quasars show that for these objects there is a strong correlation between the equivalent width of the CIV wavelength 1550 emission line and the luminosity of the underlying continuum. Assuming Friedmann cosmologies, the scatter in this correlation is a minimum for q (sub o) is approximately 1. Alternatively, luminosity evolution can be invoked to give compact distributions for q (sub o) is approximately 0 models. A sample of Seyfert galaxies observed with IUE shows that despite some dispersion the average equivalent width of CIV wavelength 1550 in Seyfert galaxies is independent of the underlying continuum luminosity. New redshifts for 4 quasars are given

Bringing closure to microlensing mass measurement

Interferometers offer multiple methods for studying microlensing events and determining the properties of the lenses. We investigate the study of microlensing events with optical interferometers, focusing on narrow-angle astrometry, visibility, and closure phase. After introducing the basics of microlensing and interferometry, we derive expressions for the signals in each of these three channels. For various forecasts of the instrumental performance, we discuss which method provides the best means of measuring the lens angular Einstein radius theta_E, a prerequisite for determining the lens mass. If the upcoming generation of large-aperture, AO-corrected long baseline interferometers (e.g. VLTI, Keck, OHANA) perform as well as expected, theta_E may be determined with signal-to-noise greater than 10 for all bright events. We estimate that roughly a dozen events per year will be sufficiciently bright and have long enough durations to allow the measurement of the lens mass and distance from the ground. We also consider the prospects for a VLTI survey of all bright lensing events using a Fisher matrix analysis, and find that even without individual masses, interesting constraints may be placed on the bulge mass function, although large numbers of events would be required.Comment: 23 pages, aastex, submitted to Ap

Garden of Roses

https://digitalcommons.library.umaine.edu/mmb-ps/2747/thumbnail.jp

Phase transition in the globalization of trade

Globalization processes interweave economic structures at a worldwide scale, trade playing a central role as one of the elemental channels of interaction among countries. Despite the significance of such phenomena, measuring economic globalization still remains an open problem. More quantitative treatments could improve the understanding of globalization at the same time that help a formal basis for comparative economic history. In this letter, we investigate the time evolution of the statistical properties of bilateral trade imbalances between countries in the trade system. We measure their cumulative probability distribution at different moments in time to discover a sudden transition circa 1960 from a regime where the distribution was always represented by a steady characteristic function to a new state where the distribution dilates as time goes on. This suggests that the rule that was governing the statistical behavior of bilateral trade imbalances until the 60's abruptly changed to a new form persistent in the last decades. In the new regime, the figures for the different years collapse into a universal master curve when rescaled by the corresponding global gross domestic product value. This coupling points to an increased interdependence of world economies and its onset corresponds in time with the starting of the last globalization wave.Comment: Final versio