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71.
72.
Fanzhi Yang Karsten Rauch Katharina Kettelhoit Lutz Ackermann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(42):11467-11470
Versatile ruthenium(II) complexes allow for site‐selective C H oxygenations with weakly‐coordinating aldehydes. The challenging C H functionalizations proceed with high chemoselectivity by rate‐determining C H metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles. 相似文献
73.
Highly Selective Dimerization and Trimerization of Isobutene to Linearly Linked Products by Using Nickel Catalysts 下载免费PDF全文
Prof. Arno Behr Nils Rentmeister Thomas Seidensticker Jonas Vosberg Dr. Stephan Peitz Dr. Dietrich Maschmeyer 《化学:亚洲杂志》2014,9(2):596-601
The unique linear linkage of isobutene to generate highly valuable C8 precursors for plasticizers is feasible by using special nickel catalysts. (4‐Cyclooctene‐1‐yl)(1,1,1,5,5,5‐hexafluoro‐2,4‐acetylacetonato)nickel and aluminum‐alkyl‐activated nickel acetylacetonates produce isobutene dimers with high selectivities of up to 95 %. Moreover, selectivity for the head‐to‐head products (2,5‐dimethylhexenes) is remarkably high at up to 99 %. Additionally, novel C12 isobutene trimers are also formed with a very high selectivity of up to 99 % for the linear linkage. The trimer structure (2,5,8‐trimethylnonenes) reflects the stepwise characteristic of the reaction mechanism. Pathways of insertion and activation and the deactivation processes of the catalyst are discussed in detail. 相似文献
74.
Maximilian Stangier Alexej Scheremetjew Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201654
Electrochemical fluorinations of C(sp3)−H bonds with a nucleophilic fluoride source have been accomplished in a chemo- and site-selective fashion, avoiding the use of electrophilic F+ sources and stoichiometric oxidants. The introduced metal-free strategy exhibits high functional group tolerance, setting the stage for late-stage fluorinations of biorelevant motifs. The synthetic utility of the C(sp3)−H fluorination was reflected by subsequent one-pot arylation of the generated benzylic fluorides. 相似文献
75.
Sebastian Wöllner Timothy Nowak Dr. Gui-Rong Zhang Dr. Nils Rockstroh Dr. Hanadi Ghanem Prof. Dr. Stefan Rosiwal Prof. Dr. Angelika Brückner Prof. Dr. Bastian J. M. Etzold 《ChemistryOpen》2021,10(5):600-606
Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) offers a renewable approach to produce the value-added platform chemical 2,5-furandicarboxylic acid (FDCA). The key for the economic viability of this approach is to develop active and selective electrocatalysts. Nevertheless, a reliable catalyst evaluation protocol is still missing, leading to elusive conclusions on criteria for a high-performing catalyst. Herein, we demonstrate that besides the catalyst identity, secondary parameters such as materials of conductive substrates for the working electrode, concentration of the supporting electrolyte, and electrolyzer configurations have profound impact on the catalyst performance and thus need to be optimized before assessing the true activity of a catalyst. Moreover, we highlight the importance of those secondary parameters in suppressing side reactions, which has long been overlooked. The protocol is validated by evaluating the performance of free-standing Cu-foam, and CuCoO modified with NaPO2H2 and Ni, which were immobilized on boron-doped diamond (BDD) electrodes. Recommended practices and figure of merits in carefully evaluating the catalyst performance are proposed. 相似文献
76.
Olena Dobrovolska
yvind Strmland
rjan Sele Handegrd Martin Jakubec Morten L. Govasli ge Aleksander Skjevik Nils ge Frystein Knut Teigen
yvind Halskau 《Molecules (Basel, Switzerland)》2021,26(12)
The driving forces and conformational pathways leading to amphitropic protein-membrane binding and in some cases also to protein misfolding and aggregation is the subject of intensive research. In this study, a chimeric polypeptide, A-Cage-C, derived from α-Lactalbumin is investigated with the aim of elucidating conformational changes promoting interaction with bilayers. From previous studies, it is known that A-Cage-C causes membrane leakages associated with the sporadic formation of amorphous aggregates on solid-supported bilayers. Here we express and purify double-labelled A-Cage-C and prepare partially deuterated bicelles as a membrane mimicking system. We investigate A-Cage-C in the presence and absence of these bicelles at non-binding (pH 7.0) and binding (pH 4.5) conditions. Using in silico analyses, NMR, conformational clustering, and Molecular Dynamics, we provide tentative insights into the conformations of bound and unbound A-Cage-C. The conformation of each state is dynamic and samples a large amount of overlapping conformational space. We identify one of the clusters as likely representing the binding conformation and conclude tentatively that the unfolding around the central W23 segment and its reorientation may be necessary for full intercalation at binding conditions (pH 4.5). We also see evidence for an overall elongation of A-Cage-C in the presence of model bilayers. 相似文献
77.
78.
We implement time propagation of the nonequilibrium Green function for atoms and molecules by solving the Kadanoff-Baym equations within a conserving self-energy approximation. We here demonstrate the usefulness of time propagation for calculating spectral functions and for describing the correlated electron dynamics in a nonperturbative electric field. We also demonstrate the use of time propagation as a method for calculating charge-neutral excitation energies, equivalent to highly advanced solutions of the Bethe-Salpeter equation. 相似文献
79.
Parmish Kaur Lukas Mai Arbresha Muriqi David Zanders Ramin Ghiyasi Dr. Muhammad Safdar Nils Boysen Manuela Winter Prof. Michael Nolan Prof. Maarit Karppinen Prof. Anjana Devi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4913-4926
Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe2, NEt2, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)3] 1 and [Yb(dpdmg)3] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O2) and water (H2O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)3] 1 was used for proof-of-principle ALD depositions of CeO2 thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO2 films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials. 相似文献
80.
Infrared Detection of Criegee Intermediates Formed during the Ozonolysis of β‐Pinene and Their Reactivity towards Sulfur Dioxide 下载免费PDF全文
Jennifer Ahrens Philip T. M. Carlsson Nils Hertl Prof. Dr. Matthias Olzmann Mark Pfeifle Dr. J. Lennard Wolf Dr. Thomas Zeuch 《Angewandte Chemie (International ed. in English)》2014,53(3):715-719
Recently, direct kinetic experiments have shown that the oxidation of sulfur dioxide to sulfur trioxide by reaction with stabilized Criegee intermediates (CIs) is an important source of sulfuric acid in the atmosphere. So far, only small CIs, generated in photolysis experiments, have been directly detected. Herein, it is shown that large, stabilized CIs can be detected in the gas phase by FTIR spectroscopy during the ozonolysis of β‐pinene. Their transient absorption bands between 930 and 830 cm?1 appear only in the initial phase of the ozonolysis reaction when the scavenging of stabilized CIs by the reaction products is slow. The large CIs react with sulfur dioxide to give sulfur trioxide and nopinone with a yield exceeding 80 %. Reactant consumption and product formation in time‐resolved β‐pinene ozonolysis experiments in the presence of sulfur dioxide have been kinetically modeled. The results suggest a fast reaction of sulfur dioxide with CIs arising from β‐pinene ozonolysis. 相似文献