The previously unknown methallylnickel 2-diorganophosphanylphenolates (R=Ph, cHex) were synthesized and found to catalyze the polymerization of ethylene. To explore the potential for ligand-tuning, a variety of P-alkyl- and P-phenyl-2-phosphanylphenols was synthesized and allowed to react with [Ni(cod)(2)] (cod=1,5-cyclooctadiene) or with NiBr(2).DME and NaH. The complexes formed in situ with [Ni(cod)(2)] are generally active as ethylene polymerization catalysts with all the ligands tested, whereas the latter systems are inactive when 2-dialkylphosphanylphenols are applied. M(w) values, ranging from about 1000 to about 100000 g mol(-1), increase for various R(2)P groups in the order R=Ph

Due to its positive effect on flame propagation in the case of a well-defined breakdown, the formation of a large-scale tumble motion is an important goal in engine development. Cycle-to-cycle variations (CCV) in the tumble position and strength however lead to a fluctuating tumble breakdown in space and time and therefore to combustion variations, indicated by CCV of the peak pressure. This work aims at a detailed investigation of the large-scale tumble motion and its interaction with the piston boundary layer during the intake stroke in a state-of-the-art gasoline engine. To allow the validation of the flow near the piston surface obtained by simulation, a new measurement technique called "Flying PIV" is applied. A detailed comparison between experimental and simulation results is carried out as well as an analysis of the obtained flow field. The large-scale tumble motion is investigated based on numerical data of multiple highly resolved intake strokes obtained using scale-resolving simulations. A method to detect the tumble center position within a 3D flow field, as an extension of previously developed 2D and 3D algorithms, is presented and applied. It is then used to investigate the phase-averaged tumble structure, its characteristics in terms of angular velocity and the CCV between the individual intake strokes. Finally, an analysis is presented of the piston boundary layer and how it is influenced by the tumble motion during the final phase of the intake stroke.

Reactions of methallylnickel bromide with 2-R2PC6H4OH 1a,b (R = Ph, cHex) and AgSbF6 furnish methallylnickel phosphinophenol hexafluoroantimonates 2a,b, which are not very stable and decay in solution at room temperature within an hour (2a) or days (2b) to tetranuclear nickel complexes 3a,b. The related cationic allylpalladium complex 4a is more stable. A crystal structure analysis gives evidence of the monomeric nature, the typical η3-coordination of the allyl group, and the coordination of the phenolic hydroxyl group to palladium. In solution the OH group is uncoordinated and underlines the hemilabile character of the phosphinophenol ligands. The allylpalladium phosphinophenol tetrafluoroborate 5a, stable as a solid, slowly decomposes in CDCl3 solution to give a dinuclear complex 6a and in THF/water as the solvent the palladium bis(phosphinophenolate) 7a. Methallylpalladium phosphinophenol acetates 8a,b, existing as phosphinophenolate acetic acid conjugates, are uncommonly stable and lose the acid on heating in a vacuum without cleavage of the methallyl group to give neutral methallylpalladium phosphinophenolates 9a,b. The labile complexes 2a and 2b proved to be highly active single-component catalysts for the conversion of ethylene to isomer mixtures of butenes, hexenes, and lower amounts of higher olefins at ambient temperature. The C6 fraction consists mainly of branched and internal olefins. 5a is less active but converts ethylene on heating under pressure to a mixture of butenes and smaller amounts of hexenes, while 8 and 9 are inactive.

No abstract

This paper presents a reconstruction of the Holocene evolution of the Inskip Peninsula in SE Queensland. The peninsula links two major dune fields, the Cooloola Sand Mass to the south and K’gari (Fraser Island) to the north. Geomorphic features of this peninsula include remnant parabolic dunes, numerous beach ridges with foredunes, and a series of spits. Together these features provide insight into Holocene coastal evolution and changing marine conditions. A remnant beach ridge/foredune complex at the northern portion of Inskip may have been connected to K’gari and a river/tidal channel near Rainbow Beach township which separated it from the Cooloola Sand Mass to the south. This channel avulsed northward in the early mid-Holocene (after 8.8 ka) with spit development from the south. This was followed by a phase of beach-ridge/foredune complex development that started by ~6.7 ka. Stratigraphic evidence from the highest and best developed parabolic dunes in the northern portion of Inskip Peninsula indicates dune development from the mid-Holocene beach complex by 4.8 ka. Beach ridges with foredunes continued to prograde but notably declined in size during the late-Holocene. In the latest Holocene (<4.8 ka) many of the late-Holocene beach ridges/foredune complexes have been truncated by a re-orientation of the shoreline and longshore sediment transport has promoted the growth of the modern spit at the northern end of the peninsula. Erosive and longshore processes continue to be highly active because of tidal interactions between Great Sandy Strait and the Coral Sea. This detailed study of Inskip Peninsula’s evolution aids significantly in future coastal management decisions, and provides evidence for World Heritage Area extension for the Cooloola Sand Mass, including the incorporation of Inskip Peninsula itself. It also contributes to the global understanding to coastal evolution in an area of strong wave and tidal interaction.

Nickel bis(2‐dialkylphosphinophenolates), detected as the spent form of organonickel 2‐dialkylphosphinophenolate catalysts for the polymerization of ethylene, were studied. In contrast to the impact of the P‐basicity on the catalyst properties, the configuration of bis(2‐dialkylphosphinophenolate) nickel is controlled only by steric effects. Small alkyl substituents favor, as do phenyl groups, square planar cis‐bis(P∩O—‐chelates) while more bulky alkyl groups lead to trans‐isomers. Dicyclohexyl‐ and tert‐butylphenylphosphino groups give rise to borderline cases. Analogous palladium complexes show a slightly smaller effect of the metal size on the cis/trans‐control. Intermediates on the way to PdII bis(P∩O—‐chelates), trans‐dichloro‐bis(phosphinophenol)‐ and chloro‐phosphinophenol phosphinophenolate palladium(II) complexes could be isolated; the crystal structure of one of the latter was determined. The nickel bis(2‐dialkylphosphinophenolates) can be activated as polymerization catalysts, to a limited extent by NiBr2·DME and sodium hydride or triethylsilane in THF, more efficiently by nBuLi or nBuLi / NiBr2·DME.

Zusammenfassung: Vier kommerzielle Reagenzien zur Bestimmung der aktivierten partiellen Thromboplastinzeit (APTT) wurden hinsichtlich ihrer Sensitivität bei der Erfassung von leichten Faktorenmängeln im endogenen Gerinnungssy-. ; sie/77 untersucht. 28. Patienten mit gesicherten endogenen Haemostasestörungen wurden unter weitgehend standardisierten Bedingungen nachuntersucht. Die Bestimmung der APTT-Werte und der Einzelfaktoren VIII:C, IX, XI und XII erfolgte innerhalb von 3 Std. nach Blutentnahme unter weitgehend standardisierten Bedingungen. Die vier untersuchten APTT-Reagenzien erfaßten unterschiedlich sensitiv die entsprechenden Gerinnungsfaktorenmängel. Die geringste Sensitivität zeigte das Reagenz APTT-4, das Ellagsäure als Aktivator enthält und in 11 Fällen keine verlängerte Gerinnungszeit ergab. Das Reagenz mit der höchsten Sensitivität ergab nur in einem Fall eine normale Gerinnungszeit bei einer Verminderung von FVIII: C auf 48 U/dl. Die Ergebnisse machen deutlich, daß die kommerziellen APTT-Reagenzien sehr unterschiedliche Faktorensensii tivitäten aufweisen, wenn der vom Hersteller angegebene Referenzbereich berücksichtigt wird. Eine bessere ; Standardisierung der APTT-Reagenzien und die Angabe von Chargen-und gerätespezifischen Normalwertj. bereichen scheint dringend erforderlich. \ Schlüsselwörter: Aktivierte partielle Thromboplastinzeit (APTT) -Sensitivität -leichte endogene HaemostasestörungSummary: · The ability of4 commercial activated partial thromboplastin time (APTT) reagents to detect mild deficiencies of coagulation factors VIIl:C, IX, XI, and XII was examined in 28 patients with proven coagulopathies. All assay procedures were performed with in 3 h after blood drawing under comprehensively standardized conditions. Sensitivities of the 4 APTT reagents to coagulation factor deficiencies differed considerably. APTT-4 utilizing ellagic acid äs contact activator was the most insensitive reagent yielding normal APTT values in 11 cases. The most sensitive reagent was APTT-1 presenting a normal coagulation time in only 1 patient with mild FVIII:C deficiency (48 U/dl). The results obtained demonstrate that commercial APTT reagents di ff er in their ability to detect mild coagulation factor deficiencies, if the normal ranges declared by the manufacturers are considered. Improved standardization of APT reagents äs well äs careful evaluation of normal ranges considering lot differences and the equipment used for determining coagulation assays are urgently required.

The Inskip Peninsula is the link between two major coastal dune fields; Fraser Island (the world's largest sand island) and the adjacent Cooloola Sand Mass. There has been a notable lack of research into the geomorphology of the sand masses and the relationship between the two dunefields. This paper presents a detailed geomorphological map of the Inskip Peninsula at a scale of 1:10,000. The Peninsula can be divided into three parts; an eastern section dominated by late Holocene strandlines and foredunes with an active spit at the northern limit of the peninsula; a central zone composed of broader foredune ridges and swales and an eastern zone comprised of remnants of older parabolic sand dunes and foredune remnants. The map provides a framework for ongoing work on landscape reconstruction.