- Synthesis, characterization and isomerization performance of micro/mesoporous materials based on H-ZSM-22 zeolite
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Micro/mesoporous materials with different mesoporosities were prepared through recrystallization of H-ZSM-22 zeolite in alkaline solution with cetyltrimethylammonium bromide template (CTAB). The structure, morphology, pore properties, acidity and isomerization performance of the catalysts by using the resulting materials were characterized and assessed. The dissolution and recrystallization procedure introduced the well-developed mesoporous structure of MCM-41 type with the meso-scale channels of about 3 nm in size on the outer surfaces of the microporous H-ZSM-22 zeolites, forming the micro/mesoporous materials, which possessed increased weak B acid sites at the pore mouths and a reduced amount of total acid sites. It is shown that the presence of well-developed mesopores could remarkably improve the selectivity to multi-branched products and suppress the side cracking reactions in n-dodecane isomerization. The micro/mesoporous Pt/ZSM-22/MCM-41 bifunctional catalyst with suitable recrystallization degree exhibits high isomerization selectivity under high conversion in long-chain n-alkane isomerization compared to the original microporous Pt/H-ZSM-22 catalyst.
- Liu, Suyao,Ren, Jie,Zhang, Huaike,Lv, Enjing,Yang, Yong,Li, Yong-Wang
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- Synthesis of telechelic olefin polymers via catalyzed chain growth on multinuclear alkylene zinc compounds
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Multinuclear alkylene zinc (MAZ) compounds of the type EtZn-(R″-Zn) n-Et (R″ = ethyl and propyl branched alkylene groups) were synthesized by a simple one-step procedure in nonpolar hydrocarbon solvents from α,ω-dienes (e.g., 1,7-octadiene or 1,9-decadiene) and diethylzinc using a bis(salicylaldiminato)Zr(IV) complex, [(2-methylcyclohexyl)N=CH(2-O- C6H3-3,5-di-tert-butyl)]2ZrMe2, as a catalyst. The MAZ serves as a divalent reversible chain-transfer agent for olefin polymerization, resulting in telechelic Zn-metalated polyolefins whose molecular weights are controllable over a wide range. The Zn-terminated telechelics serve as a polymer precursor for further reactions and can be converted into a variety of telechelic functionalized polyolefins in high yield.
- Makio, Haruyuki,Ochiai, Takashi,Mohri, Jun-Ichi,Takeda, Kouji,Shimazaki, Toshiyuki,Usui, Yoko,Matsuura, Sadahiko,Fujita, Terunori
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- Unusual pathway of the tantalum-catalyzed carboalumination reaction of alkenes with triethylaluminum
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Carboalumination of 1-alkenes (1-hexene, 1-octene, 1-decene) with Et 3Al in the presence of catalytic amounts of TaCl5 results in a mixture of 2-(R-substituted)- and 3-(R-substituted)-n-butylaluminums (1:1 ratio) in total yields of 75-85%. The TaCl5-catalyzed reaction of bicyclo[2.2.1]hept-2-ene, endo-tricyclo[5.2.1.02,6]deca-3,8-diene, and (exo/endo)-5-methylbicyclo[2.1.1]hept-2-ene with Et3Al leads to the formation of diethyl[2-exo-(2′-norbornylethyl)]aluminums in high yields. DFT calculations confirm the thermodynamic preference of the final exo product. The multistep reaction mechanisms for the formation of the resultant organoaluminums through tantalacyclopentanes as key intermediates are also discussed.
- Sultanov, Rifkat M.,Samoilova, Elena V.,Popod'Ko, Natal'Ya R.,Tulyabaev, Artur R.,Sabirov, Denis Sh.,Dzhemilev, Usein M.
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supporting information
p. 6619 - 6623
(2013/11/19)
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- A structure-activity study of Ni-catalyzed alkyl-alkyl kumada coupling. Improved catalysts for coupling of secondary alkyl halides
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A structureactivity study was carried out for Ni catalyzed alkylalkyl Kumada-type cross coupling reactions. A series of new nickel(II) complexes including those with tridentate pincer bis(amino)amide ligands (RN2N) and those with bidentate mixed amino-amide ligands (RNN) were synthesized and structurally characterized. The coordination geometries of these complexes range from square planar, tetrahedral, to square pyramidal. The complexes had been examined as precatalysts for cross coupling of nonactivated alkyl halides, particularly secondary alkyl iodides, with alkyl Grignard reagents. Comparison was made to the results obtained with the previously reported Ni pincer complex [( MeN2N)NiCl]. A transmetalation site in the precatalysts is necessary for the catalysis. The coordination geometries and spin-states of the precatalysts have a small or no influence. The work led to the discovery of several well-defined Ni catalysts that are significantly more active and efficient than the pincer complex [(MeN2N)NiCl] for the coupling of secondary alkyl halides. The best two catalysts are [(HNN)Ni(PPh3)Cl] and [(HNN)Ni(2,4-lutidine)Cl]. The improved activity and efficiency was attributed to the fact that phosphine and lutidine ligands in these complexes can dissociate from the Ni center during catalysis. The activation of alkyl halides was shown to proceed via a radical mechanism.
- Ren, Peng,Vechorkin, Oleg,Von Allmen, Kim,Scopelliti, Rosario,Hu, Xile
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supporting information; experimental part
p. 7084 - 7095
(2011/06/26)
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