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Dr. Mathias Paul Eric Detmar Dr. Maria Schlangen Dr. Martin Breugst Dr. Jörg-Martin Neudörfl Prof. Dr. Dr. Helmut Schwarz Prof. Dr. Albrecht Berkessel Prof. Dr. Mathias Schäfer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2511-2518
N-Heterocyclic carbenes (NHCs, :C ) can interact with azolium salts ( C−H+ ) by either forming a hydrogen-bonded aggregate ( CHC+ ) or a covalent C−C bond ( CCH+ ). In this study, the intramolecular NHC–azolium salt interactions of aromatic imidazolin-2-ylidenes and saturated imidazolidin-2-ylidenes have been investigated in the gas phase by traveling wave ion mobility mass spectrometry (TW IMS) and DFT calculations. The TW IMS experiments provided evidence for the formation of these important intermediates in the gas phase, and they identified the predominant aggregation mode (hydrogen bond vs. covalent C−C) as a function of the nature of the interacting carbene–azolium pairs. 相似文献
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An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties
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Dr. Lei Mei Dr. Qun‐yan Wu Dr. Li‐yong Yuan Dr. Lin Wang Shu‐wen An Zhen‐ni Xie Dr. Kong‐qiu Hu Prof. Zhi‐fang Chai Prof. Peter C. Burns Prof. Wei‐qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11329-11338
The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2)3O(OH)2]2+, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. 相似文献
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Paul Cowper Yu Jin Michael D. Turton Gabriele Kociok‐Khn Simon E. Lewis 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(7):2610-2614
Azulenesulfonium salts may be readily prepared from the corresponding azulenes by an SEAr reaction. These azulene sulfonium salts are bench‐stable species that may be employed as pseudohalides for cross‐coupling. Specifically, their application in Suzuki–Miyaura reactions has been demonstrated with a diverse selection of coupling partners. These azulenesulfonium salts possess significant advantages in comparison with the corresponding azulenyl halides, which are known to be unstable and difficult to prepare in pure form. 相似文献
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Paul Mandel 《Contemporary Physics》2013,54(5):235-246
The historical development that led to the modern concept of amplification and losing without inversion is reviewed. The two basic mechanisms for amplification without inversion and their theoretical formulation are discussed. Finally, the three experiments that confirm the occurrence of these effects are described. 相似文献
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