- Borohydride catalyzed redistribution reaction of hydrosilane and chlorosilane: A potential system for facile preparation of hydrochlorosilanes
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Various borohydrides were found to catalyze the redistribution reaction of hydrosilane and chlorosilane in different solvents to produce hydrochlorosilanes efficiently and facilely. The redistribution reaction was affected by solvent and catalyst. The substrate scope was investigated in HMPA with LiBH4 as catalyst. A possible mechanism was proposed to explain the redistribution process.
- Ai, Liqing,Chen, Yi,Li, Yongming,Xu, Caihong
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p. 17404 - 17407
(2020/06/19)
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- Facile preparation of hydrochlorosilane by alkali metal halide catalyzed Si-H/Si-Cl redistribution reaction
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Various alkali metal halides were found to catalyze the Si-H/Si-Cl redistribution reaction in different polar solvents efficiently. The scope of silane substrate was studied using KF as catalyst and 18-crown-6 as cocatalyst in DMI. The alkali metal halides catalyzed redistribution system provides a useful method to prepare hydrochlorosilanes more facilely. A possible mechanism was proposed to explain the process.
- Chen, Yi,Li, Yongming,Xu, Caihong
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supporting information
(2020/09/21)
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- Hydrodehalogenation of alkyl halides catalyzed by a trichloroniobium complex with a redox active α-diimine ligand
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A high-valent d0 niobium(v) complex, (α-diimine)NbCl3 (1), bearing a dianionic redox-active α-diimine ligand served as a catalyst for a hydrodehalogenation reaction of alkyl halides in the presence of PhSiH3. During the catalytic reaction, the redox-active α-diimine ligand allowed the complex to reversibly release and accept one-electron through switching its coordination mode between a dianionic folded form and a monoanionic planar one.
- Nishiyama, Haruka,Hosoya, Hiromu,Parker, Bernard F.,Arnold, John,Tsurugi, Hayato,Mashima, Kazushi
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supporting information
p. 7247 - 7250
(2019/07/02)
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- SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
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The invention relates to a process for the production of chlorosilanes by subjecting one or more hydndosilanes to the reaction with hydrogen chloride in the presence of at least one ether compound, and a process for the production of such hydndosilanes serving as starting materials.
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- Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.
- Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
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supporting information
p. 12580 - 12584
(2019/08/16)
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- Aerobic Co or Cu/NHPI-catalyzed oxidation of hydride siloxanes: Synthesis of siloxanols
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A highly efficient preparative method for the synthesis of siloxanols based on aerobic Co(OAc)2 or Cu(OAc)2/NHPI-catalyzed oxidation of hydride siloxanes using "green", commercially available, simple inexpensive reagents and mild reaction conditions has been proposed. This is a general reaction for the synthesis of mono-, oligo- and polymeric siloxanols with various structures (linear, branched and cyclic).
- Arzumanyan, Ashot V.,Goncharova, Irina K.,Novikov, Roman A.,Milenin, Sergey A.,Boldyrev, Konstantin L.,Solyev, Pavel N.,Tkachev, Yaroslav V.,Volodin, Alexander D.,Smol'Yakov, Alexander F.,Korlyukov, Alexander A.,Muzafarov, Aziz M.
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supporting information
p. 1467 - 1471
(2018/04/12)
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- Hydrosilane synthesis via catalytic hydrogenolysis of halosilanes using a metal-ligand bifunctional iridium catalyst
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Hydrogenolysis of various halosilanes was catalysed by iridium amido complexes to produce hydrosilanes. Selective monohydrogenolysis of di- and trichlorosilanes similarly proceeded, resulting in the formation of chlorohydrosilanes (R2SiHCl or RSiHCl2) as synthetically important building blocks for various organosilicon compounds. A mechanistic study supported the in-situ formation of an iridium hydride species as a key intermediate, which could transfer the hydride to the silicon atom through a metal–ligand bifunctional mechanism. One-pot hydrotrimethylsilylation of olefins was achieved via successive hydrogenolysis and hydrosilylation reactions starting from Me3SiCl.
- Beppu, Teruo,Sakamoto, Kei,Nakajima, Yumiko,Matsumoto, Kazuhiro,Sato, Kazuhiko,Shimada, Shigeru
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- Lewis Base Catalyzed Selective Chlorination of Monosilanes
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A preparatively facile, highly selective synthesis of bifunctional monosilanes R2SiHCl, RSiHCl2 and RSiH2Cl is reported. By chlorination of R2SiH2 and RSiH3 with concentrated HCl/ether solutions, the stepwise introduction of Si?Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si?H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.
- Sturm, Alexander G.,Schweizer, Julia I.,Meyer, Lioba,Santowski, Tobias,Auner, Norbert,Holthausen, Max C.
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supporting information
p. 17796 - 17801
(2018/11/23)
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- B(C6F5)3-Catalyzed Selective Chlorination of Hydrosilanes
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The chlorination of Si?H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si?H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O?B(C6F5)3 and HCl with the release of H2 as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O?B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.
- Chulsky, Karina,Dobrovetsky, Roman
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supporting information
p. 4744 - 4748
(2017/04/11)
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- [...] compound
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PROBLEM TO BE SOLVED: To provide a method of manufacturing a dichloromonohydrosilane compound that is capable of manufacturing a dichloromonohydrosilane compound useful as a synthesis raw material for various silane compounds such as a silane coupling agent or a functional silicone oil by using inexpensive and easily available monohydrosilane compound at a low cost since it does not require a special reaction device for conducting reactions under pressure.SOLUTION: There is provided a method of manufacturing dichloromonohydrosilane compound represented by the general formula (3) HSiRCl, where Ris an unsubstituted or a substituted monovalent hydrocarbon group having a substituent at other than α position of a silicon atom, by reacting a trichloroorganosilane compound represented by the general formula (1) RSiCl, where Ris as defined above, and a monohydrosilane compound represented by the general formula (2) HSiRCl, where Ris an unsaturated or a substituted monovalent hydrocarbon group and m is 1, 2 or 3.
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Paragraph 0041
(2020/10/21)
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- An efficient method to synthesize chlorosilanes from hydrosilanes
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An efficient, highly selective and productive synthesis of chlorosilanes from hydrosilanes is reported. Ceramic spheres were added to chlorination reaction systems and found to greatly increase the efficiency and yields of the reactions. PhSiH2Cl, PhSiHCl2, PhSiCl3, Ph 2SiHCl, Ph2SiCl2, PhMeSiHCl and PhMeSiCl 2 were synthesized from the corresponding hydrosilanes in only a few hours with yields that typically exceeded 90%. This is the first time PhSiCl3, Ph2SiHCl, Ph2SiCl2 and PhMeSiCl2 have been synthesized by this method. The factors that affect the rate of the chlorination reaction were studied. In addition the rate constant, reaction order and apparent activation energy of the chlorination reaction were also determined by kinetics study. The reaction was found to have an induction period.
- Wang, Wenchao,Tan, Yongxia,Xie, Zemin,Zhang, Zhijie
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- METHOD OF REDUCING A HALOSILANE COMPOUND IN A MICROREACTOR
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A method of producing a hydrosilane compound in a microreactor comprises reducing a halosilane compound in the microreactor and in the presence of a reducing agent to produce the hydrosilane compound.
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Paragraph 0037-0042
(2013/08/28)
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- Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
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Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
- Kunai, Atsutaka,Ohshita, Joji
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- Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
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Disclosed is a process for preparing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, comprising reacting (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound in the presence of a cyanide or a thiocyanate. The cyanide or the thiocyanate is preferably a copper salt. According to the process of the invention, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, which is very useful for the preparation of a metallocene complex catalyst component, can be prepared in a high yield for a short period of time.
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- REACTIONS OF TELLURIUM(IV) CHLORIDES WITH SOME ORGANOSILICON HYDRIDES
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The reactions of several organosilicon hydrides PhnSiH(4-n), n = 1, 2; R3SiH, R3 = Ph3, Ph2Me, PhMe2, (n-C6H13)3; (p-Me2HSi)2C6H4, with TeCl4 in benzene resulted in the formation of tellurium metal and chlorosilanes in 75-90percent yields.Similar reactions with aryltellurium trichlorides (RTeCl3, R = Ph, p-MeOC6H4, p-EtOC6H4) proceeded in two different ways.On stirring at room temperature for 6-8 h, diaryl ditellurides and chlorosilanes were obtained in 70-95percent yields whereas on refluxing for 6-10 h, tellurium powder and diaryltellurium dichlorides were obtained along withthe chlorosilanes in 80-95percent yields.Diaryltellurium dichlorides (R2TeCl2, R = Ph, p-MeOC6H4) did not react readily with PhSiH3 nor with Ph3SiH.
- Chadha, Raj K.,Drake, John E.,Neo, Mary K. H.
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