- Heterogeneous hydrosilylation reaction catalysed by platinum complexes immobilized on bipyridine-periodic mesoporous organosilicas
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The utility of a bipyridine periodic mesoporous organosilica, BPy-PMO, as a support material of a hydrosilylation catalyst was investigated in the hydrosilylation of phenylacetylene with trimethoxysilane. [PtMe2(BPy-PMO)] (1) exhibited a modera
- Naganawa, Yuki,Maegawa, Yoshifumi,Guo, Haiqing,Gholap, Sandeep Suryabhan,Tanaka, Shinji,Sato, Kazuhiko,Inagaki, Shinji,Nakajima, Yumiko
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p. 5534 - 5540
(2019/05/10)
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- Highly β(Z)-Selective Hydrosilylation of Terminal Alkynes Catalyzed by Thiolate-Bridged Dirhodium Complexes
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A series of novel monothiolate-bridged dirhodium complexes, [Cp Rh(μ-SR)(μ-Cl)2RhCp ][BF4] {Cp? = ??5-C5Me5, R = tertiary butyl (tBu), 1a; R = ferrocenyl (Fc), 1b; R = adamantyl (Ad), 1c} were designed and successfully synthesized, which can smoothly facilitate highly regioselective and stereoselective hydrosilylation of terminal alkynes to afford β(Z) vinylsilanes with good functional group compatibility. Furthermore, the hydride bridged dirhodium complex [Cp Rh(μ-StBu)(μ-Cl)(μ-H)RhCp ][BF4] (5) as a potential intermediate was obtained by the reaction of 1a with excess HSiEt3.
- Zhao, Xiangyu,Yang, Dawei,Zhang, Yahui,Wang, Baomin,Qu, Jingping
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supporting information
p. 5357 - 5361
(2018/09/13)
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- Hydrosilylation of alkynes catalysed by platinum on titania
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The heterogeneous hydrosilylation of alkynes catalysed by platinum on titania is reported. A variety of hydrosilanes react with both terminal and internal alkynes to furnish the corresponding vinyl silanes in high yields and short reaction times as well as in a regio- and stereoselective manner. The catalyst can be easily recovered and reused in several consecutive cycles.
- Alonso, Francisco,Buitrago, Robison,Moglie, Yanina,Ruiz-Martínez, Javier,Sepúlveda-Escribano, Antonio,Yus, Miguel
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experimental part
p. 368 - 372
(2011/02/16)
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- Novel immobilized hydrosilylation catalysts based on rhodium 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidenes
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The reactivity of a well defined Rh (I) complex, i.e. Rh(CF 3COO)(NHC)(COD) (1, NHC = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6- tetrahydropyrimidin-2-ylidene, COD = η4-cycloocta-1,5-diene) in the hydrosilylation of 1-alkenes, alkynes,
- Imlinger, Nicolas,Wurst, Klaus,Buchmeiser, Michael R.
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- The effect of substituents at silicon on the cross-metathesis of trisubstituted vinylsilanes with olefins
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Efficient cross-metathesis of vinylsilanes, carrying a large spectrum of different substituents at silicon, with various olefins in the presence of the first and second generation Grubbs catalyst and Hoveyda-Grubbs catalyst is described. On the basis of the results of equimolar reactions of vinylsilanes with ruthenium alkylidene complexes and experiments with deuterium-labelled reagents, a general, metallacarbene mechanism for the cross-metathesis of trisubstituted vinylsilanes with olefins has been suggested. Reaction was proved to be a valuable method for synthesis of unsaturated organosilicon derivatives.
- Pietraszuk, Cezary,Fischer, Helmut,Rogalski, Szymon,Marciniec, Bogdan
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p. 5912 - 5921
(2007/10/03)
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- Cross-coupling reaction of pentacoordinate alkenylsilicates with organic halides and triflates catalyzed by a palladium complex
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Isolated pentacoordinate alkoxy-substituted alkenylsilicates, are readily prepared by mixing alkenyltrialkoxysilane, catechol and triethylamine at room temperature.Cross-coupling reactions of these alkenylsilicates with organic halides or triflates are catalyzed by a palladium complex and proceed very smoothly and cleanly to give the corresponding alkenes.The cross-coupling reactions could be also attained by a one pot operation without isolation of pentacoordinate organosilicates.The mechanism of this cross-coupling reaction is also described here. alkoxy-substituted alkenylsilicate / pentacoordinate silicate / cross-coupling / palladium catalyst / aryl halide / aryl triflate / styrene derivative / 1,3-diene
- Hojo, Makoto,Murakami, Chikara,Aihara, Hidenori,Komori, Ei-ichi,Kohra, Shinya,et al.
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p. 499 - 508
(2007/10/02)
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- The β-Effect: Changing the Ligands on Silicon
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The ability of a silyl group to stabilize a carbocation β to silicon, the β-effect, is directly related to the electron-withdrawing ability of the groups on silicon.This was shown by using the degree of syn addition of bromine to (E)-β-silylstyrenes as a
- Brook, Michael A.,Neuy, Axel
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p. 3609 - 3616
(2007/10/02)
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- An Examination of the β-Effect in an Addition Reaction with Different Ligands on Silicon
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The degree of cis-addition of bromine to a series of β-silylstyrenes may be used to compare the ability of silicon atoms bearing a variety of different ligands to stabilize a β-carbocation.
- Brook, Michael A.,Hadi, Mahmud A.,Neuy, Axel
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p. 957 - 959
(2007/10/02)
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- RHODIUM(I)-MONO- UND -DIAZADIENEKOMPLEXE, SYNTHESE, SPEKTROSKOPISCHE CHARAKTERISIERUNG, OXIDATIVE ADDITIONSREAKTIONEN UND EINSATZ IN DER HOMOGENEN KATALYSE ZUR HYDROSILYLIERUNG
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The reaction of(Rh(CO)2Cl)2 with di- and monoazadienes gives planar, four-coordinated rhodium(I) complexes Rh(CO)Cl(DAD) (III) and Rh(CO)Cl(MAD)2 (V), respectively, which catalyse the hydrosilylation of alkenes and alkynes.In a stereoselektive cis-addition symmetric internal alkynes give the corresponding silyl alkenes, while the catalytic addition of silane to terminal alkynes leads to the 2-silyl and cis-and trans-1-silyl-alkenes; their ratio depends on the controlling ligand and on the reaction conditions.With a stoichiometric amount of the silane the complexes III react under oxidative addition to give the rhodium(III) complexes Rh(H)(SiR3)(DAD)Cl (VI), which also catalyse the hydrosilylation.
- Brockmann, Monika,Dieck, Heindirk tom,Klaus, Juergen
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p. 209 - 226
(2007/10/02)
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