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81.
Dr. Lin Xu Dr. Dawei Zhang Dr. Tanya K. Ronson Prof. Jonathan R. Nitschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(19):7505-7508
The use of di(2-pyridyl)ketone in subcomponent self-assembly is introduced. When combined with a flexible triamine and zinc bis(trifluoromethanesulfonyl)imide, this ketone formed a new Zn4L4 tetrahedron 1 bearing twelve uncoordinated pyridyl units around its metal-ion vertices. The acid stability of 1 was found to be greater than that of the analogous tetrahedron 2 built from 2-formylpyridine. Intriguingly, the peripheral presence of additional pyridine rings in 1 resulted in distinct guest binding behavior from that of 2 , affecting guest scope as well as binding affinities. The different stabilities and guest affinities of capsules 1 and 2 enabled the design of systems whereby different cargoes could be moved between cages using acid and base as chemical stimuli. 相似文献
82.
Dr. Bidyut B. Sarma Jonglack Kim Jonas Amsler Dr. Giovanni Agostini Dr. Claudia Weidenthaler Norbert Pfänder Dr. Raul Arenal Dr. Patricia Concepción Dr. Philipp Plessow Prof. Dr. Felix Studt Dr. Gonzalo Prieto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5855-5864
Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
83.
Philipp Rotering Lukas F. B. Wilm Janina A. Werra Dr. Fabian Dielmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):406-411
Electron-rich tertiary phosphines are valuable species in chemical synthesis. However, their broad application as ligands in catalysis and reagents in stoichiometric reactions is often limited by their costly synthesis. Herein, we report the synthesis and properties of a series of phosphines with 1-alkylpyridin-4-ylidenamino and 1-alkylpyridin-2-ylidenamino substituents that are accessible in a very short and scalable route starting from commercially available aminopyridines and chlorophosphines. The determination of the Tolman electronic parameter (TEP) value reveals that the electron donor ability can be tuned by the substituent pattern at the aminopyridine backbone and it can exceed that of common alkylphosphines and N-heterocyclic carbenes. The potential of the new phosphines as strong nucleophiles in phosphine-mediated transformations is demonstrated by the formation of Lewis base adducts with CO2 and CS2. In addition, the coordination chemistry of the new phosphines towards CuI, AuI, and PdII metal centers has been explored, and a convenient procedure to introduce the most basic phosphine into metal complexes starting from air-stable phosphonium salt is described. 相似文献
84.
Ferdinand H. Lutter Lucie Grokenberger Philipp Spieß Jeffrey M. Hammann Konstantin Karaghiosoff Paul Knochel 《Angewandte Chemie (International ed. in English)》2020,59(14):5546-5550
A combination of 10 % CoCl2 and 20 % 2,2′‐bipyridine ligands enables cross‐coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3‐ and 1,4‐substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with primary and secondary alkylzinc reagents providing the alkylated alkynes. 相似文献
85.
86.
Bidyut B. Sarma Jonglack Kim Jonas Amsler Giovanni Agostini Claudia Weidenthaler Norbert Pfnder Raul Arenal Patricia Concepcin Philipp Plessow Felix Studt Gonzalo Prieto 《Angewandte Chemie (International ed. in English)》2020,59(14):5806-5815
Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
87.
Philipp Wilhelm Dominik Blank Prof. John M. Lupton Dr. Jan Vogelsang 《Chemphyschem》2020,21(10):961-965
Controlling the morphology of π-conjugated polymers for organic optoelectronic devices has long been a goal in the field of materials science. Since the morphology of a polymer chain is closely intertwined with its photophysical properties, it is desirable to be able to change the arrangement of the polymers at will. We investigate the π-conjugated polymer poly(9,9-dioctylfluorene) (PFO), which can exist in three distinctly different structural phases: the α-, β-, and γ-phase. Every phase has a different chain structure and a unique photoluminescence (PL) spectrum. Due to its unique properties and the pronounced spectral structure-property relations, PFO can be used as a model system to study the morphology of π-conjugated polymers. To avoid ensemble averaging, we examine the PL spectrum of single PFO chains embedded in a non-fluorescent matrix. With single-molecule spectroscopy the structural phase of every single chain can be determined, and changes can be monitored very easily. To manipulate the morphology, solvent vapor annealing (SVA) was applied, which leads to a diffusion of the polymer chains in the matrix. The β- and γ-phases appear during the self-assembly of single α-phase PFO chains into mesoscopic aggregates. The extent of β- and γ-phase formation is directed by the solvent-swelling protocol used for aggregation. Aggregation unequivocally promotes formation of the more planar β- and γ-phases. Once these lower-energy more ordered structural phases are formed, SVA cannot return the polymer chain to the less ordered phase by aggregate swelling. 相似文献
88.
Burkart Philipp 《Nachrichten aus der Chemie》1994,42(12):1256-1258
89.
Two samples of mussels (Mytilus edulis) were collected from the southwest of Ireland. One sample contained domoic acid, the other sample contained okadaic acid,
dinophysistoxin-2 and azaspiracid-1, -2 and -3. Wet and freeze-dried reference materials were prepared from each of the two
samples to test for differences in homogeneity, stability and extractability of the analytes in either condition. Wet materials
were homogenised, aliquoted and hermetically sealed under argon and subsequently frozen at −80 °C. Dry materials were similarly
homogenised but frozen in flat cakes prior to freeze-drying. After grinding, sieving and further homogenisation, the resulting
powder was aliquoted and hermetically sealed. Domoic acid materials were characterised using HPLC–UV, while LC–MS was used
for the determination of lipophilic toxins. The extractabilities of all phycotoxins studied were comparable for wet and freeze-dried
materials once a sonication step had been carried out for reconstitution of the freeze-dried materials prior to extraction.
Homogeneity was assessed through replicate analysis of the phycotoxins (n = 10), and was found to be similar for wet and freeze-dried materials, for both hydrophilic and lipophilic toxins. Water
contents were determined for both wet and freeze-dried materials, and particle size was determined for the freeze-dried materials.
Stability was evaluated isochronously over eight months at four temperatures (−20, +4, +20 and +40 °C). The freeze-dried material
containing domoic acid was stable over the whole duration at all temperatures, while in the wet material domoic acid degraded
to some extent at all temperatures except −20 °C. In freeze-dried and wet materials containing lipophilic toxins, okadaic
acid, dinophysistoxin-2, azaspiracid-1 and azaspiracid-2 were stable over the whole duration at all conditions, while concentrations
of azaspiracid-3 changed significantly in both materials at some storage temperatures.
Figure Aliquots of freeze-dried and wet mussel tissue reference materials containing the various shellfish toxins examined in the
study 相似文献
90.
The heterogeneously catalyzed liquid phase Fries rearrangement reaction of phenyl acetate was carried out on Beta zeolites reexchanged with different amounts of metal cations. The aim of this work was to determine the influence of the amount of Brønsted acid sites as the catalytic active centers on the conversion. Sodium and potassium ions as well as divalent calcium and zinc ions were used in the reexchange procedure. The conversion shows a linear dependency on the degree of ion reexchange following the theoretically expected values. So the results prove that the bridged hydroxyl groups are indeed the dominating active centers and that their strength seems to be independent of the degree of reexchange; consequently, their acidic strength should be identical. A special emphasis was placed on the reexchange with divalent metal ions. It was shown that one divalent ion is not able to replace two protons as is supposed to be necessary for the charge balance—so a 1:1 stoichiometry is needed to assume to explain the catalytic results. 相似文献