- Access to Derivatizable Octahydrofluorenyl Ligand: Half-Sandwich Rare-Earth Metal Complexes for Highly Syndiospecific (Co)Polymerization of Styrene
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A simple and facile synthetic pathway for accessing new derivatizable bulky-demanding octahydrofluorenyl (OHF) ligands has been developed, and a series of half-sandwich rare-earth metal (Sc, Y, Lu) complexes bearing the OHF ancillary ligands have been synthesized. In conjunction with a borate, the OHF-ligated Sc complexes exhibited high catalytic activity for styrene (co)polymerization to afford polymers with highly syndiotactic polystyrene sequence (>99% rrrr).
- You, Fen,Xu, Suting,Wang, Jixing,Zhai, Jingjing,Wang, Fei,Pan, Li,So, Yat-Ming,Shi, Xiaochao
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p. 1145 - 1151
(2022/01/12)
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- Synthesis of jet fuel range high-density polycycloalkanes with polycarbonate waste
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Jet fuel range high-density polycycloalkanes were first synthesized with polycarbonate waste by a two-step method which was conducted under mild conditions. In the first step, polycarbonate waste was converted to bisphenol by methanolysis. Subsequently, bisphenol was further converted to polycycloalkanes by hydrodeoxygenation.
- Tang, Hao,Hu, Yancheng,Li, Guangyi,Wang, Aiqin,Xu, Guoliang,Yu, Cong,Wang, Xiaodong,Zhang, Tao,Li, Ning
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supporting information
p. 3789 - 3795
(2019/07/31)
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- Titanium(III)-Oxo Clusters in a Metal-Organic Framework Support Single-Site Co(II)-Hydride Catalysts for Arene Hydrogenation
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Titania (TiO2) is widely used in the chemical industry as an efficacious catalyst support, benefiting from its unique strong metal-support interaction. Many proposals have been made to rationalize this effect at the macroscopic level, yet the underlying molecular mechanism is not understood due to the presence of multiple catalytic species on the TiO2 surface. This challenge can be addressed with metal-organic frameworks (MOFs) featuring well-defined metal oxo/hydroxo clusters for supporting single-site catalysts. Herein we report that the Ti8(μ2-O)8(μ2-OH)4 node of the Ti-BDC MOF (MIL-125) provides a single-site model of the classical TiO2 support to enable CoII-hydride-catalyzed arene hydrogenation. The catalytic activity of the supported CoII-hydride is strongly dependent on the reduction of the Ti-oxo cluster, definitively proving the pivotal role of TiIII in the performance of the supported catalyst. This work thus provides a molecularly precise model of Ti-oxo clusters for understating the strong metal-support interaction of TiO2-supported heterogeneous catalysts.
- Ji, Pengfei,Song, Yang,Drake, Tasha,Veroneau, Samuel S.,Lin, Zekai,Pan, Xiandao,Lin, Wenbin
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p. 433 - 440
(2018/01/17)
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- Hydrogen Self-Sufficient Arene Reduction to Cyclohexane Derivatives Using a Combination of Platinum on Carbon and 2-Propanol
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Various arenes have been hydrogenated using platinum on carbon in a 2-propanol-aqueous mixed solvent at 100 C without the addition of flammable hydrogen gas to give the corresponding cyclohexane derivatives. 2-Propanol plays a role as an efficient hydrogen source based on the platinum on carbon-catalyzed dehydrogenation.
- Sawama, Yoshinari,Mori, Misato,Yamada, Tsuyoshi,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 3667 - 3670
(2016/01/25)
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- Acenaphthene and fluorene hydrogenation on industrial aluminum oxide catalysts in a flow system
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Hydrogenation of the tricyclic aromatic hydrocarbons acenaphthene and fluorene on industrial aluminum oxide catalysts in a flow system has been studied. It has been found that total these hydrocarbons are exhaustively hydrogenated in the presence of a nickel-chromium catalyst at 200°C and a pressure of 100 atm to give isomer mixtures of the corresponding perhydroaromatic hydrocarbons decahydroacenaphthene and dodecahydrofluorene. The liquid products obtained can be of interest as components of hydrocarbon fuels with increased density. Certain conformational features of the stereoisomers obtained have been considered. It has been assumed that some spatial isomers of decahydroacenaphthene have six-membered rings in the boat conformation.
- Bagrii,Tsodikov
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p. 100 - 104
(2014/05/06)
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- Reduction of aromatic compounds with Al powder using noble metal catalysts in water under mild reaction conditions
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In water, Al powder becomes a powerful reducing agent, transforming in cyclohexyl either one or both benzene rings of aromatic compounds such as biphenyl, fluorene and 9,10-dihydroanthracene under mild reaction conditions in the presence of noble metal catalysts, such as Pd/C, Rh/C, Pt/C, or Ru/C. The reaction is carried out in a sealed tube, without the use of any organic solvent, at low temperature. Partial aromatic ring reduction was observed when using Pd/C, the reaction conditions being 24 h and 60 °C. The complete reduction process of both aromatic rings required 12 h and 80 °C with Al powder in the presence of Pt/C.
- Rayhan, Ummey,Kwon, Hyeokmi,Yamato, Takehiko
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p. 952 - 957
(2014/08/18)
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- Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions
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An efficient and practical arene hydrogenation procedure based on the use of heterogeneous platinum group catalysts has been developed. Rh/C is the most effective catalyst for the hydrogenation of the aromatic ring, which can be conducted in iPrOH under neutral conditions and at ordinary to medium H 2 pressures (10 atm). A variety of arenes such as alkylbenzenes, benzoic acids, pyridines, furans, are hydrogenated to the corresponding cyclohexyl and heterocyclic compounds in good to excellet yields. The use of Ru/C, less expensive than Rh/C, affords an effective and practical method for the hydrogenation of arenes including phenols. Both catalysts can be reused several times after simple filtration without any significant loss of catalytic activity.
- Maegawa, Tomohiro,Akashi, Akira,Yaguchi, Kiichiro,Iwasaki, Yohei,Shigetsura, Masahiro,Monguchi, Yasunari,Sajiki, Hironao
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experimental part
p. 6953 - 6963
(2010/02/28)
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- Extractive hydrogenation: A new and versatile technique broadening gas chromatography applications
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A new technique, "extractive hydrogenation", is combined with gas chromatography (GC) to analyze organic including biological samples. In this method, the sample (or an extract thereof) is subjected to intense hydrogenation under aqueous conditions in the presence of excess (in terms of mass) palladium/carbon catalyst. Products with a saturated hydrocarbon framework result, for example, as alcohols, the larger of which adsorb onto the carbon of the catalyst. These larger products are separately recovered by extracting the washed catalyst with an organic solvent and then detected by GC. Here, the GC was fitted with a flame ionization detector (FID) or an electron impact mass spectrometer (EI-MS). Detection in this way (H2-GC) of the following trace analytes was achieved: (a) 100 μg of an (acetylamino)fluorene-deoxyguanosine DNA adduct spiked into 1 mg of DNA; (b) 1.5 μg of novobiocin, an antibiotic, spiked into 15 mL of milk (followed by extraction prior to H2-GC); and (c) 1 mg of 4-aminobiphenyl, a carcinogen, spiked into 150 mg of hemoglobin (followed by hydrolysis prior to H2-GC). The technique gave somewhat different GC-FID chromatograms for Escherichia coli and Enterococcus bacteria. Unlike pyrolysis (similarly used prior to GC), which tends to convert a biological sample into a char, the hydrogenation technique turns the sample into a clear aqueous solution. Most importantly, the method brings a broad variety of organic-containing samples in a simple way into the scope of GC/EI-MS with its computerized library of spectra.
- Itani, Mohammad,Giese, Roger W.
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p. 1189 - 1197
(2007/10/02)
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