18 results
Search Results
Now showing 1 - 10 of 18
- ItemNickel-Catalyzed Carbonylative Synthesis of Functionalized Alkyl Iodides(Amsterdam : Elsevier B.V., 2018) Peng, J.-B.; Wu, F.-P.; Xu, C.; Qi, X.; Ying, J.; Wu, X.-F.Chemistry; Catalysis; Organic Synthesis © 2018 The Author(s)Functionalized alkyl iodides are important compounds in organic chemistry and biology. In this communication, we developed an interesting nickel-catalyzed carbonylative synthesis of functionalized alkyl iodides from aryl iodides and ethers. With Mo(CO)6 as the solid CO source, both cyclic and acyclic ethers were activated, which is also a challenging topic in organic synthesis. Functionalized alkyl iodides were prepared in moderate to excellent yields with outstanding functional group tolerance. Besides the high value of the obtained products, all the atoms from the starting materials were incorporated in the final products and the reaction had high atom efficiency as well.
- ItemNaphtalenediimide-based donor-acceptor copolymer prepared by chain-growth catalyst-transfer polycondensation: Evaluation of electron-transporting properties and application in printed polymer transistors(London [u.a.] : Royal Society of Chemistry, 2014) Schmidt, G.C.; Höft, D.; Haase, K.; Hübler, A.C.; Karpov, E.; Tkachov, R.; Stamm, M.; Kiriy, A.; Haidu, F.; Zahn, D.R.T.; Yan, H.; Facchetti, A.The semiconducting properties of a bithiophene-naphthalene diimide copolymer (PNDIT2) prepared by Ni-catalyzed chain-growth polycondensation (P1) and commercially available N2200 synthesized by Pd-catalyzed step-growth polycondensation were compared. Both polymers show similar electron mobility of ∼0.2 cm2 V-1 s-1, as measured in top-gate OFETs with Au source/drain electrodes. It is noteworthy that the new synthesis has several technological advantages compared to traditional Stille polycondensation, as it proceeds rapidly at room temperature and does not involve toxic tin-based monomers. Furthermore, a step forward to fully printed polymeric devices was achieved. To this end, transistors with PEDOT:PSS source/drain electrodes were fabricated on plastic foils by means of mass printing technologies in a roll-to-roll printing press. Surface treatment of the printed electrodes with PEIE, which reduces the work function of PEDOT:PSS, was essential to lower the threshold voltage and achieve high electron mobility. Fully polymeric P1 and N2200-based OFETs achieved average linear and saturation FET mobilities of >0.08 cm2 V-1 s-1. Hence, the performance of n-type, plastic OFET devices prepared in ambient laboratory conditions approaches those achieved by more sophisticated and expensive technologies, utilizing gold electrodes and time/energy consuming thermal annealing and lithographic steps.
- ItemTheoretical mechanistic investigation of zinc(ii) catalyzed oxidation of alcohols to aldehydes and esters(London : RSC Publishing, 2016) Nisa, Riffat Un; Mahmood, Tariq; Ludwig, Ralf; Ayub, KhurshidThe mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde and ester by H2O2 oxidant was investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Both inner sphere and intermediate sphere mechanisms have been analyzed in the presence and absence of pyridine-2-carboxylic acid (ligand). An intermediate sphere mechanism involving the transfer of hydrogen from alcohol to H2O2 was found to be preferred over the competitive inner sphere mechanism involving β-hydride elimination. Kinetic barriers associated with the intermediate sphere mechanism are consistent with the experimental observations, suggesting that the intermediate sphere mechanism is a plausible mechanism under these reaction conditions. The oxidation of alcohols to aldehydes (first step) is kinetically more demanding than the oxidation of hemiacetals to esters (second step). Changing the oxidant to tert-butyl hydrogen peroxide (TBHP) increases the activation barrier for the oxidation of alcohol to aldehyde by 0.4 kcal mol−1, but decreases the activation barrier by 3.24 kcal mol−1 for oxidation of hemiacetal to ester. Replacement of zinc bromide with zinc iodide causes the second step to be more demanding than the first step. Pyridine-2-carboxylic acid ligand remarkably decreases the activation barriers for the intermediate sphere pathway, whereas a less pronounced inverse effect is estimated for the inner sphere mechanism.
- ItemBrønsted acid-catalyzed hydroarylation of activated olefins(London : RSC Publishing, 2014) Fleischer, Ivana; Pospech, JolaA mild, regiospecific Brønsted acid-catalyzed hydroarylation of activated olefins, capable of the formation of quinone methide-like intermediates, has been investigated. Variously substituted 2- and 4-vinylphenols, 4-vinylaniline or 6-vinyl-naphthalen-2-ol were successfully implemented in a sequential protonation and Friedel–Crafts-type alkylation reaction of electron-rich arenes.
- ItemPhotocatalytic degradation and toxicity evaluation of diclofenac by nanotubular titanium dioxide–PES membrane in a static and continuous setup(London : RSC Publishing, 2015) Fischer, K.; Kühnert, M.; Gläser, R.; Schulze, A.Diclofenac is a commonly used anti-inflammatory drug, which has been found in surface waters. Advanced oxidation processes (AOPs) seem to be the most suitable technique to prevent the entry of diclofenac and other pollutants into surface waters. TiO2 is especially reliable in mineralizing many organic molecules. The combination of TiO2 nanotubes with a polymer microfiltration membrane (polyethersulfone, PES) showed high photocatalytic activity by degrading diclofenac combined with an excellent membrane performance and long-term stability. By continuously degrading pollutants from water via a cross-flow setup, the molecules to be degraded are transported right to the membrane surface so that the overall reaction rate is increased. The toxicity of diclofenac was reduced by photocatalysis and photolysis; however, photocatalysis had greater impact. Moreover, the complete degradation of pollutants is very important to avoid highly toxic intermediate products.
- ItemNovel naphthylpyridines from cobalt-catalyzed cyclotrimerization of a chiral diyne(Wien [u.a.] : Springer, 2017-11-28) Trommer, Volkmar; Fischer, Fabian; Hapke, MarkoThe concise synthesis of a novel chiral diyne substrate for the assembly of chiral naphthylpyridines was described and different conditions for the cobalt-catalyzed co-cyclotrimerization with nitriles investigated. The products are novel naphthylpyridines possessing configurationally stable biaryl axes.
- ItemZnO Nanoparticles Encapsulated in Nitrogen-Doped Carbon Material and Silicalite-1 Composites for Efficient Propane Dehydrogenation(Amsterdam [u.a.] : Elsevier, 2019) Zhao, Dan; Li, Yuming; Han, Shanlei; Zhang, Yaoyuan; Jiang, Guiyuan; Wang, Yajun; Guo, Ke; Zhao, Zhen; Xu, Chunming; Li, Ranjia; Yu, Changchun; Zhang, Jian; Ge, Binghui; Kondratenko, Evgenii V.Chemistry; Catalysis; Nanoparticles © 2019 The Author(s)Non-oxidative propane dehydrogenation (PDH)is an attractive reaction from both an industrial and a scientific viewpoint because it allows direct large-scale production of propene and fundamental analysis of C-H activation respectively. The main challenges are related to achieving high activity, selectivity, and on-stream stability of environment-friendly and cost-efficient catalysts without non-noble metals. Here, we describe an approach for the preparation of supported ultrasmall ZnO nanoparticles (2–4 nm, ZnO NPs)for high-temperature applications. The approach consists of encapsulation of NPs into a nitrogen-doped carbon (NC)layer in situ grown from zeolitic imidazolate framework-8 on a Silicalite-1 support. The NC layer was established to control the size of ZnO NPs and to hinder their loss to a large extent at high temperatures. The designed catalysts exhibited high activity, selectivity, and on-stream stability in PDH. Propene selectivity of about 90% at 44.4% propane conversion was achieved at 600°C after nearly 6 h on stream. © 2019 The Author(s)
- ItemPoisoning of bubble propelled catalytic micromotors: The chemical environment matters(Cambridge [u.a.] : Royal Society of Chemistry, 2013) Zhao, G.; Sanchez, S.; Schmidt, O.G.; Pumera, M.Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.
- ItemThe Exploration of Aroyltrimethylgermane as Potent Synthetic Origins and Their Preparation(Amsterdam [u.a.] : Elsevier, 2019) Yuan, Yang; Zhang, Youcan; Chen, Bo; Wu, Xiao-FengThe synthetic utilities of acylgermanes are surprisingly rarely explored compared with their analogues. In this communication, the survey of aroyltrimethylgermane as potent synthetic origins has been studied. A variety of novel chemical transformations have been realized, including using the acylgermane group as a directing group in Rh-catalyzed aromatic C-H alkenylation reaction and Ir-catalyzed aromatic C-H amidation reactions. Additionally, a general approach for acylgermanes preparation has been established as well. The catalytic system proceeds effectively in the presence of Pd(OAc)2/BINOL-based monophosphite (L11) and allows for the straightforward access to a wide range of functionalized acylgermanes in high yields. © 2019 The Author(s)Catalysis; Organic Synthesis; Organic Reaction; Chemical Synthesis © 2019 The Author(s)
- ItemHomopolymerization of ethylene, 1-hexene, styrene and copolymerization of styrene with 1,3-cyclohexadiene using (η5- tetramethylcyclopentadienyl)dimethylsilyl(N-Ar')amido-TiCl2/MAO (Ar'=6-(2-(diethylboryl)phenyl)pyrid-2-yl, biphen-3-yl)(Basel : MDPI AG, 2011) Camadanli, S.; Decker, U.; Kühnel, C.; Reinhardt, I.; Buchmeiser, M.R.The propensity of a half-sandwich (η55- tetramethylcyclopentadienyl) dimethylsilylamido TiIV-based catalyst bearing an auxiliary diethylboryl-protected pyridyl moiety (Ti-8), activated by methylaluminoxane (MAO) to homopolymerize α-olefins such as ethylene, 1-hexene and styrene as well as to copolymerize styrene with 1,3-cyclohexadiene is described. The reactivity of Ti-8 was investigated in comparison to a 6-(2-(diethylboryl)phenyl)pyrid-2-yl-free analogue (Ti-3).