- N,N-Dimethylformamide-protected Fe2O3 Combined with Pt Nanoparticles: Characterization and Catalysis in Alkene Hydrosilylation
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We report a combination of N,N-dimethylformamide (DMF)-protected Fe2O3 nanoparticles (NPs) and Pt NPs for the hydrosilylation of various industrially relevant alkenes and tertiary silanes. The DMF-protected Fe2O3 and Pt NPs catalysts were characterized by transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. The catalyst of DMF-protected Fe2O3 NPs combined with Pt NPs can be recycled for five cycles by a simple extraction using hexane/DMF. The developed combination Fe2O3/Pt NPs catalyst is effective up to the 1-kilogram scale.
- Kanda, Yasuharu,Kondo, Ryota,Lin, Xianjin,Nagata, Tatsuki,Obora, Yasushi,Shimizu, Ken-ichi,Suzuki, Takeyuki,Tanaka, Tatsuya,Toyao, Takashi
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- High catalytic activity and selectivity in hydrosilylation of new Pt(II) metallosupramolecular complexes based on ambidentate ligands
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Two new air- and water-stable Pt(II) metallosupramolecular complexes based on ambidentate ligands have been designed, synthesized and fully characterized. The structure of complexes has been determined by various analytical techniques including NMR spectroscopy and TOF-MS. Additionally, the single crystal structure of 2 was determined by X-ray diffraction. The catalytic activity of these complexes in hydrosilylation has been investigated, establishing that both have similar high activity and selectivity within a broad scope of structurally distinct olefins and hydrosilanes.
- Walczak, Anna,Stachowiak, Hanna,Kurpik, Gracjan,Ka?mierczak, Joanna,Hreczycho, Grzegorz,Stefankiewicz, Artur R.
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p. 139 - 146
(2019/04/08)
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- METHOD FOR PRODUCING ORGANOSILICON COMPOUND BY HYDROSILYLATION WITH METALLIC-ELEMENT-CONTAINING NANOPARTICLES
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An organosilicon compound can be efficiently produced by using metallic element-containing nanoparticles such as a platinum element-containing nanoparticle having a solvent on surface as a catalyst of the hydrosilylation reaction of alkenes.
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Paragraph 0091-0095
(2019/11/21)
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- Careful investigation of the hydrosilylation of olefins at poly(ethylene glycol) chain ends and development of a new silyl hydride to avoid side reactions
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Hydrosilylation of olefin groups at poly(ethylene glycol) chain ends catalyzed by Karstedt catalyst often results in undesired side reactions such as olefin isomerization, hydrogenation, and dehydrosilylation. Since unwanted polymers obtained by side reactions deteriorate the quality of end-functional polymers, maximizing the hydrosilylation efficiency at polymer chain ends becomes crucial. After careful investigation of the factors that govern side reactions under various conditions, it was related that the short lifetime of the unstable Pt catalyst intermediate led to the formation of more side products under the inherently dilute conditions for polymers. Based on these results, two new chelating hydrosilylation reagents, tris(2-methoxyethoxy)silane (5) and 2,10-dimethyl-3,6,9-trioxa-2,10-disilaundecane (6), have been developed. It was demonstrated that the hydrosilylation efficiency at polymer chain ends was significantly increased by employing the internally coordinating hydrosilane 5. In addition, employment of the internally coordinating disilane species 6 in an addition polymerization with 1,5-hexadiene by hydrosilylation reaction yielded a polymer with high molecular weight (Mn = 9300 g/mol), which was significantly higher than that (Mn = 2600 g/mol) of the corresponding polymer obtained with non-chelating dihydrosilane, 1,1,3,3-tetramethyldisiloxane.
- Shin, Hyunseo,Moon, Bongjin
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p. 527 - 536
(2018/01/27)
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- Thiols make for better catalysts: Au nanoparticles supported on functional SBA-15 for catalysis of Ullmann-type homocouplings
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A strategy for arraying small gold nanoparticles on a mesoporous support modified with single-component or mixed self-assembled monolayers is described. The use of mixed surface modifiers allows easy access to a range of surface chemistries and modalities of interaction between nanoparticles and supports. A combination of thiol groups and linear semifluorinated chains effectively stabilized the nanoparticles against aggregation, while preserving their catalytic activity. The thiol-fluorous-supported catalyst was found active in Ullmann-type homocoupling of aryl halides and showed exceptional selectivity in this reaction.
- Chen, Tianyou,Chen, Ba-Tian,Bukhryakov, Konstantin V.,Rodionov, Valentin O.
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supporting information
p. 11638 - 11641
(2017/11/03)
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- An Easily Accessed Nickel Nanoparticle Catalyst for Alkene Hydrosilylation with Tertiary Silanes
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The first efficient and non-precious nanoparticle catalyst for alkene hydrosilylation with commercially relevant tertiary silanes has been developed. The nickel nanoparticle catalyst was prepared in situ from a simple nickel alkoxide precatalyst Ni(OtBu)2?x KCl. The catalyst exhibits high activity for anti-Markovnikov hydrosilylation of unactivated terminal alkenes and isomerizing hydrosilylation of internal alkenes. The catalyst can be applied to synthesize a single terminal alkyl silane from a mixture of internal and terminal alkene isomers, and to remotely functionalize an internal alkene derived from a fatty acid.
- Buslov, Ivan,Song, Fang,Hu, Xile
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supporting information
p. 12295 - 12299
(2016/10/13)
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- Application of polyethyleneglycol (PEG) functionalized ionic liquids for the rhodium-catalyzed hydrosilylation reaction of alkenes
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Abstract Rh(PPh3)3Cl-polyethyleneglycol (PEG) functionalized ionic liquids with various anions were used as a catalytic system for the hydrosilylation reaction of alkenes. The influence of the anion of the ionic liquid has been investigated. It was found that the anion has an impact on the catalytic activity and selectivity. [PEG400DIL][PF6]-[Rh(PPh3)3Cl] shows an improved catalytic performance towards the hydrosilylation reaction of alkenes. The scope of alkenes and recycling of the catalytic system have been investigated.
- Bai, Ying,Zhang, Fengxiang,Li, Jiayun,Xu, Yisong,Peng, Jiajian,Xiao, Wenjun
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- MCM-41-immobilised bidentate nitrogen platinum complex: A highly efficient and recyclable phosphine-free catalytic system for the hydrosilylation of olefins
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An MCM-41-immobilised bidentate nitrogen platinum complex (MCM-41-2N-Pt) was very conveniently synthesised from commercially available and cheap 3-(2-aminoethylamino)propyltrimethoxysilane by immobilisation on the mesoporous silica nanoparticles, MCM-41, followed by reaction with potassium chloroplatinite. It was found that the MCM-41-2N-Pt complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be easily recovered and reused several times without significant loss of activity.
- Zhang, Hean,Liu, Jiaqin,Cheng, Shaojuan,Cai, Mingzhong
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experimental part
p. 241 - 243
(2012/09/08)
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- MCM-41-supported bidentate phosphine rhodium complex: An efficient and recyclable heterogeneous catalyst for the hydrosilylation of olefins
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MCM-41-supported bidentate phosphine rhodium complex (MCM-41-2P-RhCl 3) was conveniently synthesized from commercially available and cheapγ-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.
- Hu, Ronghua,Hao, Wenyan,Cai, Mingzhong
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experimental part
p. 1629 - 1634
(2012/01/13)
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- A novel fumed silica-supported nitrogenous platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane
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A novel fumed silica-supported nitrogenous platinum complex was conveniently prepared from cheap γ-aminopropyltriethoxysilane via immobilization on fumed silica in toluene, followed by a reaction with hexachloroplatinic acid. The title complex was characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the complex is an efficient and stable catalyst for the hydrosilylation of olefins with triethoxysilane. The title platinum complex could be separated by simple filtration and reused several times without any appreciable loss in the catalytic activity. Crown Copyright
- Li, Ji,Yang, Chunhui,Zhang, Lei,Ma, Tianlong
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experimental part
p. 1845 - 1849
(2011/06/19)
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- A diphosphino-functionalised MCM-41-anchored platinum complex: An efficient and reusable catalyst for the hydrosilylation of olefins
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A diphosphino-functionalised MCM-41 anchored platinum complex (MCM-41-2P-Pt) was conveniently synthesised from commercially available and cheap γ-aminopropyltriethoxysilane via immobilisation on MCM-41, followed by reactiopn with diphenylphosphinomethanol and potassium chloroplatinite. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive reactionss without any decrease in activity.
- Zha, Lingfang,Hao, Wenyan,Cai, Mingzhong
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experimental part
p. 648 - 652
(2011/03/18)
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- MCM-41-supported mercapto platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane
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A novel MCM-41-supported mercapto platinum complex was conveniently synthesized from commercially available and cheap γ-mercaptopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with potassium chloroplatinite. The powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the title platinum complex. It was found that the title complex is an efficient catalyst for hydrosilylation of olefins with triethoxysilane and can be reused several times without noticeable loss of activity.
- Hu, Ronghua,Zha, Lingfang,Cai, Mingzhong
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scheme or table
p. 563 - 566
(2010/08/05)
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- Hydrosilylation of olefins over rhodium complex anchored over thioether-functionalized MCM-41
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The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 °C in the presence of 0.01. mol% of thioether-functionalized MCM-41 anchored rhodium complex, affording the corresponding addition products in 68-91% yields. This supported rhodium complex can be reused several times without noticeable loss of activity. Our system not only solves the basic problems of catalyst separation and recovery, but also avoids the use of phosphine ligands.
- Zha, Lig Fang,Yang, Wei Sen,Hao, Wen Yan,Cai, Ming Zhong
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experimental part
p. 1310 - 1313
(2011/10/09)
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- METHOD FOR EXTENDING LONG-TERM ELECTRICAL POWER CABLE PERFORMANCE
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An improved method for imparting excellent long-term dielectric performance to an in-service electrical cable section having a stranded conductor surrounded by a conductor shield encased in a polymeric insulation and having an interstitial void volume in the region of the conductor, the cable section having an average operating temperature T. The method comprising injecting a dielectric enhancement fluid composition into the interstitial void volume, the composition comprising at least one component selected from: (1) a water-reactive material selected from an organosilane monomer, the above organosilane monomer wherein at least one of the water-reactive groups has been substituted with a condensable silanol group, an oligomer of the above organosilane monomer, or a co-oligomer of the above organosilane monomer, the organosilane monomer having a diffusion coefficient at least about 15 times greater than the diffusion coefficient of its corresponding tetramer;(2) a water-reactive material similar to (1) having at least one group attached to silicon comprising 7 to about 20 —CH2— units;(3) a non-water-reactive organic material which has a diffusion coefficient of less than about 10?9 cm2/sec and an equilibrium concentration of at least about 0.005 gm/cm3 in the polymeric insulation, the above mentioned diffusion coefficients and equilibrium concentration being determined at temperature T; or(4) an organic compound having an equilibrium concentration in the polymeric insulation at 55° C. which is less than 2.25 times the equilibrium concentration at 22° C.
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