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991.
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Dr. David Schweinfurth Marcella Mazzolini Dr. Dmytro Neshchadin Carolin Hoyer Roman Geier Dr. Karl Gatterer Dr. Nils Trapp Prof. Dr. Georg Gescheidt Prof. Dr. François Diederich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(21):7152-7157
The synthesis of redox‐active p‐ and o‐quinones 2‐phenylamino‐4‐phenylimino[6]helicene‐1‐one 1 , 2‐phenylamino[6]‐helicene‐1,4‐dione 2 , and 4‐phenyl[6]helicene‐1,2‐dione 3 in their enantiopure forms by post‐functionalization of (P)‐ and (M)‐1,2‐dimethoxy[6]helicene is presented. Structural characterization in solution and in the solid state was accomplished by 2D NMR spectroscopy methods and X‐ray diffraction analysis, respectively. Interpretation of electrochemical redox data was accompanied by a detailed orbital picture, derived from DFT calculations. The electronic structures of compounds 1 – 3 were investigated by UV/Vis and electronic circular dichroism (ECD) spectroscopy, complemented by TD‐DFT calculations. Quinones 1 – 3 were chemically reduced to study the EPR signatures of their respective radical anions. DFT methods were used for the atom assignment of the hyperfine coupling constants. The results are discussed within the context of electrochromic chiral switches and molecular recognition. 相似文献
994.
995.
Push–Pull Buta‐1,2,3‐trienes: Exceptionally Low Rotational Barriers of Cumulenic CC Bonds and Proacetylenic Reactivity 下载免费PDF全文
Przemyslaw Gawel Dr. Yi‐Lin Wu Dr. Aaron D. Finke Dr. Nils Trapp Dr. Michal Zalibera Prof. Dr. Corinne Boudon Dr. Jean‐Paul Gisselbrecht Dr. W. Bernd Schweizer Prof. Dr. Georg Gescheidt Prof. Dr. François Diederich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6215-6225
A variety of asymmetrically donor–acceptor‐substituted [3]cumulenes (buta‐1,2,3‐trienes) were synthesized by developed procedures. The activation barriers to rotation ΔG≠ were measured by variable temperature NMR spectroscopy and found to be as low as 11.8 kcal mol?1, in the range of the barriers for rotation around sterically hindered single bonds. The central C?C bond of the push–pull‐substituted [3]cumulene moiety is shortened down to 1.22 Å as measured by X‐ray crystallography, leading to a substantial bond length alternation (BLA) of up to 0.17 Å. All the experimental results are supported by DFT calculations. Zwitterionic transition states (TS) of bond rotation confirm the postulated proacetylenic character of donor–acceptor [3]cumulenes. Additional support for the proacetylenic character of these chromophores is provided by their reaction with tetracyanoethene (TCNE) in a cycloaddition‐retroelectrocyclization (CA–RE) cascade characteristic of donor‐polarized acetylenes. 相似文献
996.
Georg Berschneider 《Monatshefte für Mathematik》2012,166(3-4):329-340
In this paper we consider bounded, conditionally positive definite functions on commutative hypergroups. We show an integral representation that allows to decompose conditionally positive definite functions as differences of positive definite functions. 相似文献
997.
Georg Berschneider 《Monatshefte für Mathematik》2012,43(1):329-340
In this paper we consider bounded, conditionally positive definite functions on commutative hypergroups. We show an integral representation that allows to decompose conditionally positive definite functions as differences of positive definite functions. 相似文献
998.
Dr. Tobias Böttcher Simon Steinhauer Dr. Lesley C. Lewis‐Alleyne Beate Neumann Dr. Hans‐Georg Stammler Dr. Bassem S. Bassil Prof. Dr. Gerd‐Volker Röschenthaler Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):893-899
The addition of BCl3 to the carbene‐transfer reagent NHC→SiCl4 (NHC=1,3‐dimethylimidazolidin‐2‐ylidene) gave the tetra‐ and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3]+ and [(NHC)2SiCl3]+ with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ? OEt2, on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2F5)2SiCl2 was treated with NHC→SiCl4. In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3]+ and [(NHC)2SiCl3]+ were detected with [(C2F5)SiCl3]? as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2F5)2SiH2, which gave [(NHC)2SiCl2H][(C2F5)SiCl3]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2F5)2Cl2 and NHC→Si(C2F5)2ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron‐poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4, and may even serve as a carbene‐transfer reagent as well. 相似文献
999.
Chemoenzymatic Synthesis of Nonasulfated Tetrahyaluronan with a Paramagnetic Tag for Studying Its Complex with Interleukin‐10 下载免费PDF全文
Sebastian Köhling Georg Künze Katharina Lemmnitzer Dr. Marcel Bermudez Prof. Dr. Gerhard Wolber Dr. Jürgen Schiller Prof. Dr. Daniel Huster Prof. Dr. Jörg Rademann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5563-5574
Implants and artificial biomaterials containing sulfated hyaluronans have been shown to improve the healing of injured skin and bones. It is hypothesized that these effects are mediated by the binding of sulfated glycosaminoglycans (GAGs) to growth factors and cytokines, resulting in the sequestering of proteins to the wound healing site and in modulated protein activity. Given that no direct synthetic access to sulfated oligohyaluronans has been available, little is known about their protein binding and the structure of the resulting protein complexes. Here, the chemoenzymatic preparation of oligohyaluronans on the gram scale is described. Oligohyaluronans are converted into anomeric azides at the reducing end, enabling the attachment of analytical labels through an anomeric ligation reaction. A nonasulfated tetrahyaluronan–ethylenediaminetetraacetic acid derivative has been produced and used as a paramagnetic tag for the elucidation of the complex of this ligand with interleukin‐10 using paramagnetic relaxation enhancement NMR analysis. The metal ion position is resolved with 1.0 Å, enabling a refined structural model of the complex. 相似文献
1000.