449 research outputs found

    Counteranion and Solvent Assistance in Ruthenium-Mediated Alkyne to Vinylidene Isomerizations

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    The complex [Cp*RuCl(iPr2PNHPy)] (1) reacts with 1-alkynes HC≡CR (R = COOMe, C6H4CF3) in dichloromethane furnishing the corresponding vinylidene complexes [Cp*Ru≡C≡CHR(iPr2PNHPy)]Cl (R = COOMe (2a- Cl), C6H4CF3 (2b-Cl)), whereas reaction of 1 with NaBPh4 in MeOH followed by addition of HC≡CR (R = COOMe, C6H4CF3) yields the metastable π-alkyne complexes [Cp*Ru(η2-HC≡CR)(iPr2PNHPy)][BPh4] (R = COOMe (3a-BPh4), C6H4CF3 (3b-BPh4)). The transformation of 3a-BPh4/3b-BPh4 into their respective vinylidene isomers in dichloromethane is very slow and requires hours to its completion. However, this process is accelerated by addition of LiCl in methanol solution. Reaction of 1 with HC≡CR (R = COOMe, C6H4CF3) in MeOH goes through the intermediacy of the π-alkyne complexes [Cp*Ru(η2-HC≡CR)(iPr2PNHPy)]Cl (R = COOMe (3a-Cl), C6H4CF3 (3b-Cl)), which rearrange to vinylidenes in minutes, i.e., much faster than their counterparts containing the [BPh4]− anion. The kinetics of these isomerizations has been studied in solution by NMR. With the help of DFT studies, these observations have been interpreted in terms of chloride- and methanolassisted hydrogen migrations. Calculations suggest participation of a hydrido−alkynyl intermediate in the process, in which the hydrogen atom can be transferred from the metal to the ÎČ-carbon by means of species with weak basic character acting as proton shuttles

    North American extreme precipitation events and related large-scale meteorological patterns: a review of statistical methods, dynamics, modeling, and trends

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    This paper surveys the current state of knowledge regarding large-scale meteorological patterns (LSMPs) associated with short-duration (less than 1 week) extreme precipitation events over North America. In contrast to teleconnections, which are typically defined based on the characteristic spatial variations of a meteorological field or on the remote circulation response to a known forcing, LSMPs are defined relative to the occurrence of a specific phenomenon-here, extreme precipitation-and with an emphasis on the synoptic scales that have a primary influence in individual events, have medium-range weather predictability, and are well-resolved in both weather and climate models. For the LSMP relationship with extreme precipitation, we consider the previous literature with respect to definitions and data, dynamical mechanisms, model representation, and climate change trends. There is considerable uncertainty in identifying extremes based on existing observational precipitation data and some limitations in analyzing the associated LSMPs in reanalysis data. Many different definitions of "extreme" are in use, making it difficult to directly compare different studies. Dynamically, several types of meteorological systems-extratropical cyclones, tropical cyclones, mesoscale convective systems, and mesohighs-and several mechanisms-fronts, atmospheric rivers, and orographic ascent-have been shown to be important aspects of extreme precipitation LSMPs. The extreme precipitation is often realized through mesoscale processes organized, enhanced, or triggered by the LSMP. Understanding of model representation, trends, and projections for LSMPs is at an early stage, although some promising analysis techniques have been identified and the LSMP perspective is useful for evaluating the model dynamics associated with extremes.11Ysciescopu

    North American extreme precipitation events and related large-scale meteorological patterns: a review of statistical methods, dynamics, modeling, and trends

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    This paper surveys the current state of knowledge regarding large-scale meteorological patterns (LSMPs) associated with short-duration (less than 1 week) extreme precipitation events over North America. In contrast to teleconnections, which are typically defined based on the characteristic spatial variations of a meteorological field or on the remote circulation response to a known forcing, LSMPs are defined relative to the occurrence of a specific phenomenon-here, extreme precipitation-and with an emphasis on the synoptic scales that have a primary influence in individual events, have medium-range weather predictability, and are well-resolved in both weather and climate models. For the LSMP relationship with extreme precipitation, we consider the previous literature with respect to definitions and data, dynamical mechanisms, model representation, and climate change trends. There is considerable uncertainty in identifying extremes based on existing observational precipitation data and some limitations in analyzing the associated LSMPs in reanalysis data. Many different definitions of "extreme" are in use, making it difficult to directly compare different studies. Dynamically, several types of meteorological systems-extratropical cyclones, tropical cyclones, mesoscale convective systems, and mesohighs-and several mechanisms-fronts, atmospheric rivers, and orographic ascent-have been shown to be important aspects of extreme precipitation LSMPs. The extreme precipitation is often realized through mesoscale processes organized, enhanced, or triggered by the LSMP. Understanding of model representation, trends, and projections for LSMPs is at an early stage, although some promising analysis techniques have been identified and the LSMP perspective is useful for evaluating the model dynamics associated with extremes.11Ysciescopu

    Unresolved issues and new challenges in teaching English to young learners:the case of South Korea

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    The introduction of languages, especially English, into the primary curriculum around the world has been one of the major language-in-education policy developments in recent years. In countries where English has been compulsory for a number of years, the question arises as to what extent the numerous and well-documented challenges faced by the initial implementation of early language learning policies have been overcome and whether new challenges have arisen as policies have become consolidated. This article therefore focuses on South Korea, where English has been compulsory in primary school since 1997. The issues raised by the introduction of English into the primary curriculum are reviewed and the current situation in South Korea is investigated. The results of a mixed methods study using survey data from 125 Korean primary school teachers, together with data from a small-scale case study of one teacher are presented. The study shows that, while some of the initial problems caused by the introduction of early language learning appear to have been addressed, other challenges persist. Moreover, the data reveal the emergence of a number of new challenges faced by primary school teachers of English as they seek to implement government policy

    Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

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    Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

    Present day greenhouse gases could cause more frequent and longer Dust Bowl heatwaves

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    Substantial warming occurred across North America, Europe and the Arctic over the early twentieth century1, including an increase in global drought2, that was partially forced by rising greenhouse gases (GHGs)3. The period included the 1930s Dust Bowl drought4,5,6,7 across North America’s Great Plains that caused widespread crop failures4,8, large dust storms9 and considerable out-migration10. This coincided with the central United States experiencing its hottest summers of the twentieth century11,12 in 1934 and 1936, with over 40 heatwave days and maximum temperatures surpassing 44 °C at some locations13,14. Here we use a large-ensemble regional modelling framework to show that GHG increases caused slightly enhanced heatwave activity over the eastern United States during 1934 and 1936. Instead of asking how a present-day heatwave would behave in a world without climate warming, we ask how these 1930s heatwaves would behave with present-day GHGs. Heatwave activity in similarly rare events would be much larger under today’s atmospheric GHG forcing and the return period of a 1-in-100-year heatwave summer (as observed in 1936) would be reduced to about 1-in-40 years. A key driver of the increasing heatwave activity and intensity is reduced evaporative cooling and increased sensible heating during dry springs and summers
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