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81.
Dr. Francesco Della Monica Dr. Veronica Paradiso Prof. Dr. Alfonso Grassi Dr. Stefano Milione Prof. Dr. Luigi Cavallo Prof. Dr. Carmine Capacchione 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5347-5353
A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers. 相似文献
82.
Dr. Karl P. J. Gustafson Arnar Guðmundsson Dr. Éva G. Bajnóczi Dr. Ning Yuan Prof. Xiaodong Zou Prof. Ingmar Persson Prof. Jan-E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3411-3419
The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed. 相似文献
83.
Dr. Taku Kitanosono Prof. Dr. Shū Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9408-9429
Ever-evolving catalyst advances in synthetic protocols using water as a reaction medium have enriched the understanding of sustainable organic chemistry. Because conventional classification and definitions were ambivalent, it is proposed here that catalytic reactions using water be collectively called to be “in water”, with further classification into seven types. When accelerated in water as heterogeneous mixtures, the reactions can be regarded as following an “on-water” mechanism. The original term “on water” coined by Sharpless is incongruous with catalytic reactions, whereas on-water used in this review covers all the interfaces involving water where chemical reactions are accelerated. As a result of the unconcluded dispute on the antiquated catalyst-free “on water” model, the modified model defines three water layers: water molecules that are oriented to extrude protons toward the oil phase in the inner layer, those enwrapped by a secondary layer, and finally the bulk water layer. In light of the latitudinous outlook on the role of water at the interface, selected examples of reactions, in particular those reported over the past decade, that follow an “on-water” mechanism are reviewed herein. 相似文献
84.
Dr. Youai Qiu Alexej Scheremetjew Dr. Lars H. Finger Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3241-3246
Electrophotochemistry has enabled arene C−H trifluoromethylation with the Langlois reagent CF3SO2Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF3 radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C−H trifluoromethylations of unactivated arenes and heteroarenes. The robust nature of the electrophotochemical manifold was reflected by a wide scope, including electron-rich and electron-deficient benzenes, as well as naturally occurring heteroarenes. Electrophotochemical C−H trifluoromethylation was further achieved in flow with a modular electro-flow-cell equipped with an in-operando monitoring unit for on-line flow-NMR spectroscopy, providing support for the single electron transfer processes. 相似文献
85.
Fangyuan Zhou Lesong Li Kao Lin Feng Zhang Prof. Dr. Guo-Jun Deng Dr. Hang Gong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(19):4246-4250
The radical–radical coupling reaction is an important synthetic strategy. In this study, the iron-catalyzed radical–radical cross-coupling reaction based on the decarboxylation of keto acids and decarbonylation of aliphatic aldehydes to obtain valuable aryl ketones is reported for the first time. Remarkably, when tertiary aldehydes were used as carbonyl sources, ketone esters were selectively obtained instead of ketones. The gram-scale preparation of aryl ketone through this strategy was easily achieved by using only 3 mol % of the iron catalyst. As a proof-of-concept, the bioactive molecule flurprimidol was synthesized in two steps by using this strategy. 相似文献
86.
Dr. Yiteng Zheng Ziyu Tang Prof. Simon G. Podkolzin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5174-5179
The development of improved technologies for biomass processing into transportation fuels and industrial chemicals is hindered due to a lack of efficient catalysts for selective oxygen removal. Here we report that platinum nanoparticles decorated with subnanometer molybdenum clusters can efficiently catalyze hydrodeoxygenation of acetic acid, which serves as a model biomass compound. In contrast with monometallic Mo catalysts that are inactive and monometallic Pt catalysts that have low activities and selectivities, bimetallic Pt–Mo catalysts exhibit synergistic effects with high activities and selectivities. The maximum activity occurs at a Pt to Mo molar ratio of three. Although Mo atoms themselves are catalytically inactive, they serve as preferential binding anchors for oxygen atoms while a catalytic transformation proceeds on neighboring surface Pt atoms. Beyond biomass processing, Pt–Mo nanoparticles are promising catalysts for a wide variety of reactions that require a transformation of molecules with an oxygen atom and, more broadly, in other fields of science and technology that require tuning of surface–oxygen interactions. 相似文献
87.
Zhenxiong Huang Dr. Xiangjiu Guan Prof. Mingtao Li Prof. Liejin Guo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(31):7118-7123
Akaganeite (β-FeOOH) is a widely investigated candidate for photo(electro)catalysis, such as water splitting. Nevertheless, insights into understanding the surface reaction between water and β-FeOOH, in particular, the hydrogen evolution reaction (HER), are still insufficient. Herein, a set of first-principles calculations on pristine β-FeOOH and halogen-substituted β-FeOOH are applied to evaluate the HER performance through the computational hydrogen electrode model. The results show that the HER on β-FeOOH tends to occur at Fe sites on the (010) surface, and palladium and nickel are found to serve as excellent co-catalysts to boost the HER process, due to the remarkably reduced free energy change of hydrogen adsorption upon loading on the surface of β-FeOOH, demonstrating great potential for efficient water splitting. 相似文献
88.
Xiaojuan Liu Qingqing Wen Prof. Dr. Li Xiang Dr. Xuebing Leng Prof. Dr. Yaofeng Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5494-5499
The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6-(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields. 相似文献
89.
Dr. Abdessamad Grirrane Dr. Eleuterio Álvarez Prof. Dr. Hermenegildo García Prof. Dr. Avelino Corma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8810-8818
The cationic complex [(JohnPhos–Au)3(acetylide)][SbF6] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide–trigold(I)–JohnPhos system; the trinuclear–acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η1,η2,η1 coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)2] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [AuIL1][SbF6] complexes in CH2Cl2 at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [CuIL1][PF6] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established. 相似文献
90.
Dr. Ruofei Cheng Prof. Dr. Zaozao Qiu Prof. Dr. Zuowei Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7212-7218
Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]2-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration. 相似文献