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Friedrich Kreyenschmidt Selim E. Meurer Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5912-5921
>The combination of CoCl2 with bidentate phosphines is known to catalyze challenging cross-coupling and Heck-type reactions, but the mechanisms of these valuable transformations have not been established. Here, we use electrospray-ionization mass spectrometry to intercept the species formed in these reactions. Our results indicate that a sequence of transmetalation, reductive elimination, and redox disproportionation convert the cobalt(II) precatalyst into low-valent cobalt complexes. These species readily transfer single electrons to alkyl bromides, which thereupon dissociate into alkyl radicals and Br−. In cross-coupling reactions, the alkyl radicals add to the cobalt catalyst to form observable heteroleptic complexes, which release the coupling products through reductive eliminations. In the Heck-type reactions, the low abundance of newly formed ionic species renders the analysis more difficult. Nonetheless, our results also point to the occurrence of single-electron transfer processes and the involvement of radicals in these transformations. 相似文献
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The theory of physical dimensions and units in physics is outlined. This includes a discussion of the universal applicability and superiority of quantity equations. The International System of Units (SI) is one example thereof. By analyzing mechanics and electrodynamics, it naturally leads one, besides the dimensions of length and time, to the fundamental units of action , electric charge q, and magnetic flux ?. Also, and are known. These results of classical physics suggests to look into the corresponding quantum aspects of q and ? (and also of ): The electric charge occurs exclusively in elementary charges e, whereas the magnetic flux can have any value; in specific situations, however, in superconductors of type II at very low temperatures, ? appears quantized in the form of fluxons (Abrikosov vortices). And leads, of course, to the Planck quantum h. Thus, one is directed to superconductivity and, because of the resistance, to the quantum Hall effect. In this way, the Josephson and the quantum Hall effects come into focus quite naturally. One goal is to determine the behavior of the fundamental constants in special and in general relativity. 相似文献
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Susanne Schmidt Friedrich Hammerschmidt 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Phosphorylation of various aliphatic alcohols gives phosphates 1 which are deprotonated by sBuLi/TMEDA in diethyl ether, THF or hexane at ?78 °C. The organo-lithiurns 2 and 4 formed isornerize to α-hydroxy- phosphonates 3 and 5 (phosphate-phosphonate rearrangement[1.2] 相似文献
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ABSTRACT: BACKGROUND: Archerfish show very short behavioural latencies in response to falling prey. This raises the question, which response parameters of retinal ganglion cells to moving stimuli are best suited for fast coding of stimulus speed and direction. RESULTS: We compared stimulus reconstruction quality based on the ganglion cell response parameters latency, first interspike interval, and rate. For stimulus reconstruction of moving stimuli using latency was superior to using the other stimulus parameters. This was true for absolute latency, with respect to stimulus onset, as well as for relative latency, with respect to population response onset. Iteratively increasing the number of cells used for reconstruction decreased the calculated error close to zero. CONCLUSIONS: Latency is the fastest response parameter available to the brain. Therefore, latency coding is best suited for high speed coding of moving objects. The quantitative data of this study are in good accordance with previously published behavioural response latencies. 相似文献