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1.
In a 2:2 reaction with silver(I) chloride or bromide, 1,5-bis(1-phospholano)pentane ( 1a ) afforded frame-like macrocyclic structures, with intra- ( 2 , Cl) or intermolecular ( 3 , Br) halido bridges. In contrast, 1,7-bis(1-phospholano)heptane ( 1b ) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis-phospholane and halido ligands. A unique paddle wheel-type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X-ray crystallography. 相似文献
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Laurens Kooijman Dr. Matthias Schuster Christian Baumann Simon Jurt Dr. Frank Löhr Dr. Boris Fürtig Prof. Dr. Peter Güntert Prof. Dr. Oliver Zerbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21151-21158
To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR. 相似文献
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Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides
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Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
5.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry
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Timm Bergholz Dr. Benjamin Oelkers Dr. Benedikt Huber Prof. Bernhard Roling Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2613-2620
New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C2N5]? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C2N5]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries. 相似文献
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