O,N,N-Pincer ligand effects on oxidatively induced carbon–chlorine coupling reactions at palladium

The syntheses of two families of sterically tuneable O,N,N pro-ligands are reported, namely the 2-(phenyl-2′-ol)-6-imine-pyridines, 2-(C6H4-2′-OH),6-(CMe[double bond, length as m-dash]NAr)C5H3N [Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)] and the 2-(phenyl-2′-ol)-6-(amino-prop-2-yl)pyridines, 2-(C6H4-2′-OH),6-(CMe2NHAr)C5H3N [Ar = 4-i-PrC6H4 (HL2a), 2,6-i-Pr2C6H3 (HL2b)], using straightforward synthetic approaches and in reasonable overall yields. Interaction of HL1a/c and HL2a/b with palladium(II) acetate affords the O,N,N-pincer complexes, [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), which can be readily converted to their chloride derivatives, [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (4a), 2,6-i-Pr2C6H3 (4b)), respectively, on reaction with an aqueous sodium chloride solution. Treating each of 3a, 3b, 4a and 4b with two equivalents of di-p-tolyliodonium triflate at 100 °C in a toluene/acetonitrile mixture affords varying amounts of 4-chlorotoluene along with the 4-iodotoluene by-product with the conversions highly dependent on the steric and backbone properties of the pincer complex employed (viz.4a > 3a > 4b > 3b); notably, the least sterically bulky and most flexible amine-containing 4a reaches 90% conversion to 4-chlorotoluene in 15 h as opposed to 17% for imine-containing 3b. In the case of 3a, the inorganic palladium species recovered from the reaction has been identified as the Pd(II) salt [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]N(4-i-PrC6H4)C5H3N}Pd(NCMe)][O3SCF3] (5a), which was independently prepared by the reaction of 3a with silver triflate in acetonitrile. Single crystal X-ray structures are reported for HL1a, HL2a, 1a, 1b, 2a, 2b, 3a and 5a

The Effectiveness of Visual Input Enhancement Across Multiple Proficiency Levels on the Noticing and L2 Development of German Vocabulary and Reading

The present study investigates the effectiveness of visual input enhancement across multiple proficiency levels on the noticing and L2 development of German vocabulary and reading. The study addresses several methodological issues in the extant literature and uses a complex organization to investigate possible differences in the effectiveness of visual input enhancement, a frequently used technique in L2 reading, across multiple proficiency levels in a typical L2 classroom setting at the university level. The study reveals that little to no differences exist across proficiency level and text level and that visual input enhancement, as is so often employed, has extremely limited potential for positive effects on L2 learners. In contrast, it is revealed to cause more harmful effects as opposed to aiding learners. The study also makes use of copious learner protocols to gain deeper insight into their thought processes while reading L2 texts to gauge their overall understanding and ability to acquire vocabulary

Organo-palladium(II) complexes bearing unsymmetrical N,N,N-pincer ligands: synthesis, structures and oxidatively induced coupling reactions

The 2-(2'-aniline)-6-imine-pyridines, 2-(C6H4--2'-NH2)-6-(CMe=NAr)C5H3 N (Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)), have been synthesised via sequential Stille cross-coupling, deprotection and condensation steps from 6-tributylstannyl-2-(2-methyl-1,3-dioxolan-2-yl)pyridine and 2-bromonitrobenzene. The palladium(II) acetate N,N,N-pincer complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)), can be prepared by reacting HL1 with Pd(OAc) 2 or, in the case of 1a , more conveniently by the template reaction of ketone 2-(C6H4-2'-NH2)-6-(CMe=O)C5H3N, Pd(OAc)2 and 4-isopropylaniline; ready conversion of 1 to their chloride analogues, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), has been demonstrated. The phenyl-containing complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdPh] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)), can be obtained by treating HL1 with (PPh3)2 PdPh(Br) in the presence of NaH or with regard to 3a, by the salt elimination reaction of 2a with phenyllithium

Multiple shifts and fractional integration in the us and uk unemployment rates

This paper analyses the long-run behaviour of the US and UK unemployment rates by testing for possibly fractional orders of integration and multiple shifts using a sample of over 100 annual observations. The results show that the orders of integration are higher than 0 in both series, which implies long memory. If we assume that the underlying disturbances are white noise, the values are higher than 0.5, i.e., nonstationary. However, if the disturbances are autocorrelated, the orders of integration are in the interval (0, 0.5), implying stationarity and mean-reverting behaviour. Moreover, when multiple shifts are taken into account, unemployment is more persistent in the US than in the UK, implying the need for stronger policy action in the former to bring unemployment back to its original level

Bistability of Slow and Fast Traveling Waves in Fluid Mixtures

The appearence of a new type of fast nonlinear traveling wave states in binary fluid convection with increasing Soret effect is elucidated and the parameter range of their bistability with the common slower ones is evaluated numerically. The bifurcation behavior and the significantly different spatiotemporal properties of the different wave states - e.g. frequency, flow structure, and concentration distribution - are determined and related to each other and to a convenient measure of their nonlinearity. This allows to derive a limit for the applicability of small amplitude expansions. Additionally an universal scaling behavior of frequencies and mixing properties is found. PACS: 47.20.-k, 47.10.+g, 47.20.KyComment: 4 pages including 5 Postscript figure

Legal determinants of external finance revisited : the inverse relationship between investor protection and societal well-being

This paper investigates relationships between corporate governance traditions and quality of life as measured by a number of widely reported indicators. It provides an empirical analysis of indicators of societal health in developed economies using a classification based on legal traditions. Arguably the most widely cited work in the corporate governance literature has been the collection of papers by La Porta et al. which has shown, inter alia, statistically significant relationships between legal traditions and various proxies for investor protection. We show statistically significant relationships between legal traditions and various proxies for societal health. Our comparative evidence suggests that the interests of investors may not be congruent with the interests of wider society, and that the criteria for judging the effectiveness of approaches to corporate governance should not be restricted to financial metrics

A brief introduction to recent developments in population-based structural health monitoring

This is the final version. Available from the publisher via the DOI in this record.One of the main problems in data-based Structural Health Monitoring (SHM), is the scarcity of measured data corresponding to damage states in the structures of interest. One approach to solving this problem is to develop methods of transferring health inferences and information between structures in an identified population—Population-based SHM (PBSHM). In the case of homogenous populations (sets of nominally-identical structures, like in a wind farm), the idea of the form has been proposed which encodes information about the ideal or typical structure together with information about variations across the population. In the case of sets of disparate structures—heterogeneous populations—transfer learning appears to be a powerful tool for sharing inferences, and is also applicable in the homogenous case. In order to assess the likelihood of transference being meaningful, it has proved useful to develop an abstract representation framework for spaces of structures, so that similarities between structures can formally be assessed; this framework exploits tools from graph theory. The current paper discusses all of these very recent developments and provides illustrative examplesEngineering and Physical Sciences Research Council (EPSRC

Global stability properties of a hyperbolic system arising in pattern formation

Global stability properties of a hyperbolic system arising in pattern formatio

Galaxy evolution by color-log(n) type since redshift unity in the Hubble Ultra Deep Field

We explore the use of the color-log(n) plane (where n is the global Sersic index) as a tool for subdividing the high redshift galaxy population in a physically-motivated manner. Using a series of volume-limited samples out to z=1.5 in the Hubble Ultra Deep Field (UDF) we confirm the correlation between color-log(n) plane position and visual morphology observed locally and in other high redshift studies in the color and/or structure domain. Via comparison to a low redshift sample from the Millennium Galaxy Catalogue we quantify evolution by color-log(n) type, accounting separately for the specific selection and measurement biases against each. Specifically, we measure decreases in B-band surface brightness of 1.57 +/- 0.22 mag/sq.arcsec and 1.65 +/- 0.22 mag/sq.arcsec for `blue, diffuse' and `red, compact' galaxies respectively between redshift unity and the present day.Comment: 12 pages, 6 figures, to be published in A&A (accepted 29/10/08

Evolution of avalanche conducting states in electrorheological liquids

Charge transport in electrorheological fluids is studied experimentally under strongly nonequlibrium conditions. By injecting an electrical current into a suspension of conducting nanoparticles we are able to initiate a process of self-organization which leads, in certain cases, to formation of a stable pattern which consists of continuous conducting chains of particles. The evolution of the dissipative state in such system is a complex process. It starts as an avalanche process characterized by nucleation, growth, and thermal destruction of such dissipative elements as continuous conducting chains of particles as well as electroconvective vortices. A power-law distribution of avalanche sizes and durations, observed at this stage of the evolution, indicates that the system is in a self-organized critical state. A sharp transition into an avalanche-free state with a stable pattern of conducting chains is observed when the power dissipated in the fluid reaches its maximum. We propose a simple evolution model which obeys the maximum power condition and also shows a power-law distribution of the avalanche sizes.Comment: 15 pages, 6 figure