- A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
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Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
- Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
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supporting information
p. 601 - 606
(2021/01/13)
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- Platinum-Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3-Dienes and a Butatriene
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The 1:2 reaction of [μ-(dmpm)Pt(nbe)]2 (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl2BNR(SiMe3) (R=tBu, SiMe3) yields unsymmetrical (N-aminoboryl)aminoboryl PtI2 complexes by B?N coupling via ClSiMe3 elimination. A subsequent intramolecular ClSiMe3 elimination from the tBu-derivative leads to cyclization of the BNBN unit, forming a unique 1,3,2,4-diazadiboretidin-2-yl ligand. In contrast, the analogous reaction with Br2BN(SiMe3)2 leads, via a twofold BrSiMe3 elimination, to a PtII2 A-frame complex bridged by a linear BNBN isostere of butatriene. Structural and computational data confirm π electron delocalization over the entire BNBN unit.
- Arrowsmith, Merle,Braunschweig, Holger,Brunecker, Carina,Fantuzzi, Felipe
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supporting information
p. 16864 - 16868
(2021/06/28)
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- METHOD FOR PRODUCING HALOSILANE
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PROBLEM TO BE SOLVED: To provide a method for producing halosilane that can efficiently produce halosilane. SOLUTION: Alkoxy halomethane is used as a halogenating agent and reacted with oxysilane having a structure represented by formula (a), to efficiently produce halosilane having a structure represented by formula (b) (In the formula (b), X is a chlorine atom, a bromine atom, or an iodine atom). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0028; 0035; 0036
(2019/07/31)
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- A preparation method of the trimethyl chlorosilane (by machine translation)
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The invention provides a preparation method of the trimethyl chlorosilane, six-hexamethyl disilane, double-(trichloromethyl) carbonate, catalyst is added to the solvent, thereby obtaining a reaction mixture, said reaction mixture is added to the initiator, the reaction is carried out, after the reaction is finished after treatment can get trimethylchlorosilane. The method of the invention is safe and controllable, and easy to operate, is friendly to the environment, the resulting high purity of the product, by-product is only carbon dioxide gas, the elimination of industrial production in significant corrosion source - hydrogen chloride, greatly improve the working environment in the production process, and the solvent, catalyst and initiator can be used repeatedly, is a green-friendly chlorination process, has wide industrial application prospect, is suitable for application. (by machine translation)
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Paragraph 0020-0033
(2019/05/02)
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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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Page/Page column 36; 37
(2019/04/16)
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- DISILANE-, CARBODISILANE-AND OLIGOSILANE CLEAVAGE WITH CLEAVAGE COMPOUND ACTING AS CATALYST AND HYDROGENATION SOURCE
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The invention relates to a process for the manufacture of monosilanes of formula (I): MexSiHyClz (I), comprising: the step of subjecting a silane substrate (methyldisilanes, methyloligosilanes, or carbodisilanes) to a cleavage reaction of the silicon-silicon bond(s) or the silicon- carbon bonds in silane substrates the reaction involving a cleavage compound selected from a quaternary Group 15 onium compound R4 QX, a heterocyclic amine, a heterocyclic ammonium halide, or a mixture of R3P and RX. The starting material disilanes to be cleaved has the formula (II): MemSi2HnClo (II) The starting material oligosilanes to be cleaved have the general formula (III): MepSiqHrCIs (II I), The starting material carbodisilanes to be cleaved have the general formula (IV): (MeaSiHbCle)-CH2-(MecSiHdClf) (IV)
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Page/Page column 39; 40
(2019/04/16)
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- Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents
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Nickel-catalyzed cross-coupling reactions of chlorosilanes with organoaluminum reagents were developed. An electron-rich Ni(0)/PCy3 complex was found to be an effective catalyst for the desired transformation. The reaction of dichlorosilanes 1 proceeded to give the corresponding monosubstituted products 2. Trichlorosilanes 4 underwent selective double substitution to furnish the corresponding monochlorosilanes 2. Overall, the selective synthesis of a series of alkylmonochlorosilanes 2 from di- and trichlorosilanes was achieved using the present catalytic systems.
- Naganawa, Yuki,Guo, Haiqing,Sakamoto, Kei,Nakajima, Yumiko
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p. 3756 - 3759
(2019/09/12)
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- Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
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The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4?n (n=1–3) generates a disilane residue (MenSi2Cl6?n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.
- Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
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supporting information
p. 3809 - 3815
(2019/02/13)
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- CLEAVAGE OF METHYLDISILANES TO METHYLMONOSILANES
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The invention relates to a process for the manufacture of methylmonosilanes comprising the step of subjecting one or more methyldisilanes to the cleavage reaction of the silicon-silicon bond, and optionally a step of separating the resulting methylmonosilanes.
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Page/Page column 29
(2019/04/16)
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- Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
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The industrial production of monosilanes MenSiCl4?n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6?n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si?Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.
- Sturm, Alexander G.,Santowski, Tobias,Schweizer, Julia I.,Meyer, Lioba,Lewis, Kenrick M.,Felder, Thorsten,Auner, Norbert,Holthausen, Max C.
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supporting information
p. 8499 - 8502
(2019/06/13)
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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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- Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
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The industry-scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6-n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono- and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride.
- Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
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supporting information
p. 13202 - 13207
(2019/10/22)
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- SILYLAMINE COMPOUND, COMPOSITION FOR DEPOSITING SILICON-CONTAINING THIN FILM CONTAINING THE SAME, AND METHOD FOR MANUFACTURING SILICON-CONTAINING THIN FILM USING THE COMPOSITION
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Provided are a silylamine compound, a composition for depositing a silicon-containing thin film containing the same, and a method for manufacturing a silicon-containing thin film using the composition, and more particularly, to a silylamine compound capable of being usefully used as a precursor of a silicon-containing thin film, a composition for depositing a silicon-containing thin film containing the same, and a method for manufacturing a silicon-containing thin film using the composition.
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-
Paragraph 0068; 0069
(2019/04/16)
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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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- Silacyclophanones 2*. Cyclic organosilicon esters of terephthalic acid
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[Figure not available: see fulltext.] The reactions of dichlorodimethylsilane or 1,3-dichlorotetramethyldisiloxane with bis(trimethylsilyl) ester of terephthalic acid (1:1 molar ratio, 20°C, 72–144 h) gave 69–97% yields of previously unknown 27- and 22-me
- Basenko, Sergey V.,Soldatenko, Anastasiya S.,Vashchenko, Olexandr V.,Smirnov, Vladimir I.
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p. 826 - 828
(2018/10/20)
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- Unsupported metal silyl ether coordination
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Simple silyl ethers like O(SiMe3)2 in contrast to normal ethers are inert to metal bonding; however, a “naked”, highly Lewis-acidic, cationic Mg species enforces complexation. DFT calculations indicate that agostic interactions and van der Waals attraction significantly contribute to the stability of this first example of unsupported metal silyl ether coordination.
- Pahl, Jürgen,Elsen, Holger,Friedrich, Alexander,Harder, Sjoerd
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supporting information
p. 7846 - 7849
(2018/07/25)
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- New aspects of isocyanate synthesis with the use of O-silylurethanes
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Silyl group at the nitrogen atom in the O-silylurethanes drastically affects the thermolysis processes and allows one to simplify the synthesis of methyl- and trimethylsilyl isocyanates.
- Kirilin, Aleksei D.,Belova, Liya O.,Pletneva, Maria V.,Golub, Nataliya A.,Storozhenko, Pavel A.,Kirilina, Nadezhda I.
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- Hydrodechlorination of (CH3)3SiCHCl2 over Pd, Ni, Co and Fe supported on AlF3
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Gas phase hydrodechlorination (HDC) process of Me3SiCHCl 2 was studied in a flow reactor at 200 °C using a 2% metal loading (w/w) of four different monometallic catalysts (Pd/AlF 3, Ni/AlF 3,Co/AlF 3 and Fe/AlF 3). The catalysts were prepared by sol-gel method and structurally examined by BET method, FT-IR and XPS techniques. The XPS technique showed that Ni II, Fe III and Co III exist as oxides. The major products in the HDC process of Me 3SiCHCl 2 were identified by GC and GC-MS and found to include Me 3SiCH 2Cl, Me 3SiCl, and Me 4Si. The effect of these catalysts on the quantitative conversion, selectivity and conversion rates are reported. [Figure not available: see fulltext.]
- Hina, Rateb,Arafa, Isam,Ennab, Omar
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p. 353 - 358
(2017/03/23)
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- Concerning the Role of Supercritical Carbon Dioxide in SN1 Reactions
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A series of SN1-type reactions has been studied under various conditions to clarify the role of supercritical carbon dioxide (scCO2) as reaction medium for this kind of transformations. The application of scCO2 did not result in higher yields in any of the experiments in comparison to those under neat conditions or in the presence of other inert compressed gases. High-pressure UV/Vis spectroscopic measurements were carried out to quantify the degree of carbocation formation of a highly SN1-active alkyl halide as a function of the applied solvent. No measureable concentration of carbocations could be detected in scCO2, just like in other low polarity solvents. Taken together, these results do not support the previously claimed activating effect via enhanced SN1 ionization due to the quadrupolar moment of the supercritical fluid.
- Qiao, Yun X.,Theyssen, Nils,Eifert, Tobias,Liauw, Marcel A.,Franciò, Giancarlo,Schenk, Karolin,Leitner, Walter,Reetz, Manfred T.
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supporting information
p. 3898 - 3902
(2017/03/27)
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- 1-Chloro-1,3-dimethyl-1,3-diorganyl-3-(trimethylsilylamino)disiloxanes
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The main products of the reaction of 1,3-dichloro-1,3-dimethyl-1,3-diorganyldisiloxanes with hexamethyldisilazane (molar ratio 1 : 1, 20 °C) are the earlier unknown linear 1-chloro-1,3-dimethyl-1,3-diorganyl-3-(trimethylsilylamino)disiloxanes of the general formula ClMeRSiOSiMeRNHSiMe3 (1) (R = ClCH2 (a), Me (b), Vin (c), Ph (d)) obtained in up to 53—72% yield and 1,3-dimethyl-1,3-diorganyl-1,3-bis(trimethylsilylamino)disiloxanes of the general formula (Me3SiNH)MeRSiOSiMeR(NHSiMe3) (2a—d) (7—12% yield). Thermolysis of compounds 1a—d leads to the formation of cyclic silazaoxanes. A plausible scheme for their formation was suggested.
- Basenko,Soldatenko
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p. 1074 - 1077
(2017/10/31)
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- Palladium-Nanoparticles-Catalyzed Oxidative Annulation of Benzamides with Alkynes for the Synthesis of Isoquinolones
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A novel method to synthesize isoquinolones via oxidative annulation of N-alkoxy benzamides and alkynes using binaphthyl-stabilized palladium nanoparticles (Pd-BNP) as catalyst has been developed. This methodology affords various isoquinolone derivatives in good to excellent yields with high regioselectivities in the presence of air as oxidant. N-Methoxybenzothioamide was also found to undergo oxidative annulation with alkyne successfully and provided a sulfur analogue of isoquinolones in moderate yields. The Pd-BNP catalyst was easily recovered and reused up to four times without any apparent agglomeration. (Figure presented.).
- Sharma, Nidhi,Saha, Rajib,Parveen, Naziya,Sekar, Govindasamy
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supporting information
p. 1947 - 1958
(2017/06/09)
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- One-Step Synthesis of Siloxanes from the Direct Process Disilane Residue
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The well-established Müller–Rochow Direct Process for the chloromethylsilane synthesis produces a disilane residue (DPR) consisting of compounds MenSi2Cl6?n(n=1–6) in thousands of tons annually. Technologically, much effort is made to retransfer the disilanes into monosilanes suitable for introduction into the siloxane production chain for increase in economic value. Here, we report on a single step reaction to directly form cyclic, linear, and cage-like siloxanes upon treatment of the DPR with a 5 m HCl in Et2O solution at about 120 °C for 60 h. For simplification of the Si?Si bond cleavage and aiming on product selectivity the grade of methylation at the silicon backbone is increased to n≥4. Moreover, the HCl/Et2O reagent is also suitable to produce siloxanes from the corresponding monosilanes under comparable conditions.
- Neumeyer, Felix,Auner, Norbert
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supporting information
p. 17165 - 17168
(2016/11/23)
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- Reductive silylation of Cp?UO2(MesPDIMe) promoted by Lewis bases
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Functionalization of the uranyl moiety (UO22+) in Cp?UO2(MesPDIMe) (1-PDI) (MesPDIMe = 2,6-((Mes)NCMe)2C5H3N; Mes = 2,4,6-triphenylmethyl), which bears a reduced, monoanionic pyridine(diimine) ligand, is reported. Silylating reagents, R3Si-X (R = Me, X = Cl, I, OTf, SPh; R = Ph, X = Cl), effectively add across the strong OUO bonds in the presence of the Lewis base, OPPh3, generating products of the form (R3SiO)2UX2(OPPh3)2 (R = Me, X = I (2-OPPh3), Cl (3-OPPh3), SPh (5-OPPh3), OTf (6-OPPh3); R = Ph, X = Cl (4-OPPh3)). During this transformation, reduction to uranium(iv) occurs with loss of (Cp?)2 and MesPDIMe, each of which acts as a one-electron source. In the reaction, the Lewis base serves to activate the silyl halide, generating a more electrophilic silyl group, as determined by 29Si NMR spectroscopy, that undergoes facile transfer to the oxo groups. Complete U-O bond scission was accomplished by treating the uranium(iv) disiloxide compounds with additional silylating reagent, forming the family (Ph3PO)2UX4. All compounds were characterized by 1H NMR, infrared, and electronic absorption spectroscopies. X-ray crystallographic characterization was used to elucidate the structures of 2-OPPh3, 4-OPPh3, 5-OPPh3, and 6-OPPh3.
- Kiernicki,Harwood,Fanwick,Bart
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p. 3111 - 3119
(2016/02/20)
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- 2-Halo-2-organyl-4H-benzo[d][1,3,2]dioxasilin-4-ones
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[Figure not available: see fulltext.] Original method has been developed for the preparation of previously unknown cyclic organosilicon esters of salicylic acid, containing halogen-silicon bonds. This method is based on the reaction of trimethylsilyl ester of 2-(trimethylsiloxy)benzoic acid with organylhalosilanes RR1SiXY under mild conditions, where R, R1 = Cl, Me, CH=CH2, Ph; X, Y = Cl, F.
- Basenko, Sergey V.,Zelenkov, Lev E.
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p. 295 - 298
(2016/01/12)
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- Amorphous silicon: New insights into an old material
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Amorphous silicon is synthesized by treating the tetrahalosilanes SiX4 (X=Cl, F) with molten sodium in high boiling polar and non-polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine-containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO-H versus the Me-OH bond either yields H- and/or methyl-substituted methoxy functional silanes. Moreover, compounds, such as MenSi(OMe)4-n (n=0-3) are simply accessible in more than 75% yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes MenSi(OMe)4-n in excellent (n=0:100%) to acceptable yields (n=1:51%; n=2:27%); the yield of HSi(OMe)3 is about 85%. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon-based products. Amorphous silicon is easily synthesized from tetrahalosilanes SiX4 (X=Cl, F) and molten sodium in different solvents. Reactivity studies prove the resulting materials as versatile tools for the formation of technical important silanes, such as the silicon chloro-, alkoxy-, and methylalkoxy-substituted derivatives (see figure; bl=black, br=brown).
- Spomer, Natalie,Holl, Sven,Zherlitsyna, Larissa,Maysamy, Fariba,Frost, Andreas,Auner, Norbert
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p. 5600 - 5616
(2015/03/30)
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- Synthesis and structure of potentially biologically active N-(silylmethyl)tetrahydropyrimidin-2-ones
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A transsilylation of 1,3-bis(trimethylsilyl)tetrahydropyrimidin-2-one with (chloromethyl)-chlorosilanes ClCH2SiMenCl3-n (n = 0, 2) gave the corresponding 1,3-bis[(chlorosilyl)-methyl]tetrahydropyrimidin-2-ones. New Si-containing tetrahydropyrimidin-2-ones were synthesized by the exchange reactions at the Si - Cl and Si - N bonds of these compounds. The structures of all the synthesized compounds were confirmed by multinuclear NMR spectroscopy. Virtual screening using the PASS program showed that these compounds can exhibit certain types of biological activity with 40 - 94% probability.
- Lazareva,Lazarev
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p. 2081 - 2086
(2015/06/08)
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- PROCESS FOR THE PRODUCTION OF SILANE PRODUCTS FROM CALCIUM SILICIDE
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A process for preparing a reaction product including a silane product includes step (i), (ii), and (iii). Step (i) is contacting an organohalide with a calcium silicide at a temperature from 300 °C to 700 °C to form the reaction product including a spent reactant and the silane product. The silane product has formula RmHnSiX(4-m-n), where each R is independently a monovalent organic group, each X is independently a halogen atom; subscript m is 0 to 4; subscript n is 0 to 2; and a quantity (m + n) is 0 to 4. Step (ii) is contacting, at a temperature from 200 °C to 1400 °C, the spent reactant with a silane of formula HaRbSiX(4-a-b), where subscript a is 0 to 4, subscript b is 0 or 1, a quantity (a + b) ≤ 4. The silane of formula HaRbSiX(4-a-b) is distinct from the silane product of formula RmHnSiX(4-m-n). When the quantity (a + b) 2; thereby forming a reactant. Step (iii) is contacting the reactant formed in step (ii) with an additional organohalide at a temperature from 300 °C to 700 °C to form an additional silane product of formula RmHnSiX(4-m-n). Steps (ii) and (iii) are performed separately and consecutively after step (i).
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Paragraph 0052
(2014/11/11)
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- METHOD FOR PREPARING AN ORGANO-FUNCTIONAL SILANE
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A process includes reacting an organometallic cuprate and a silicon precursor in the presence of a solvent. The process produces a reaction product including an organo-functional silane.
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Paragraph 0026
(2014/05/24)
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- Efficient organic light-emitting diodes with low efficiency roll-off at high brightness using iridium emitters based on 2-(4-trifluoromethyl-6-fluoro phenyl)pyridine and tetraphenylimidodiphosphinate derivatives
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Using 2-(4-trifluoromethyl-6-fluorophenyl)pyridine (tfmfppy) as the cyclometalated ligand and tetraphenylimidodiphosphinate (tpip) derivatives as ancillary ligands, three iridium complexes (1: Ir(tfmfppy)2tpip; 2: Ir(tfmfppy)2ftpip, ftpip = tetra(4-fluorophenyl)imidodiphosphinate; 3: Ir(tfmfppy)2tfmtpip, tfmtpip = tetra(4-trifluoromethylphenyl) imidodiphosphinate) showing phosphorescence at 514, 513 and 508 nm in CH 2Cl2 were synthesized, respectively. By using these complexes as emitters, the organic light emitting diodes with the concise configuration of indium tin oxides/1,1-bis(4-(di-p-tolyl-amino)phenyl) cyclohexane (60 nm)/1 or 2 or 3: bis[3,5-di(9H-carbazol-9-yl)phenyl]di-phenyl silane (8 wt%, 30 nm)/1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (90 nm)/lithium fluoride (1 nm)/aluminium (100 nm) showed bright green light with maximum luminance higher than 40 000 cd m-2. The maximum current efficiency (ηc) values for 1, 2 and 3 based devices (GIr1, GIr2 and GIr3) were 77.49, 66.57, and 53.26 cd A-1 at relatively high brightness of 8025, 5286 and 5169 cd m-2, respectively. In addition, the efficiency roll-off ratios from the peak efficiency to the brightness of 10 000 cd m-2 are less than 10% for all the devices. We believe that the good electron mobilities of the phosphorescent emitters lead to the high devices efficiency and low efficiency roll-off. The results suggest that these complexes have potential application in organic light emitting diodes.
- Teng, Ming-Yu,Zhang, Song,Jin, Yi-Ming,Li, Tian-Yi,Liu, Xuan,Xu, Qiu-Lei,Lin, Chen,Zheng, You-Xuan,Wang, Leyong,Zuo, Jing-Lin
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p. 105 - 113
(2014/03/21)
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- Controllably oxidized copper flakes as multicomponent copper-based catalysts for the Rochow reaction
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The metallic Cu flakes prepared by milling metallic Cu powder were controllably oxidized in air at different temperatures to obtain the Cu-based catalysts containing multicomponents of Cu, Cu2O, and CuO. These catalysts are explored in the Rochow reaction using silicon powder and methyl chloride (MeCl) as reactants to produce dimethyldichlorosilane (M2), which is the most important organosilane monomer in the industry. The samples were characterized by X-ray diffraction, temperature-programmed reduction, thermogravimetric analysis, oxidimetry analysis, particle size analysis, transmission electron microscopy, and scanning electron microscopy. Compared to the metallic Cu powder and Cu flakes, the controllably oxidized Cu flakes containing Cu, Cu2O, and CuO species show much higher M2 selectivity and silicon conversion in the Rochow reaction. The enhanced catalytic performance may stem from the larger interfacial contact among the gas MeCl, solid Si particles, and solid Cu-based catalyst flakes, as well as the synergistic effect among the different Cu species. The work would be helpful to the development of novel Cu-based catalysts for organosilane synthesis.
- Liu, Shaomian,Wang, Yingli,Zhu, Yongxia,Wang, Guangna,Zhang, Zailei,Che, Hongwei,Jia, Lihua,Su, Fabing
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p. 7826 - 7833
(2014/02/14)
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- PROCESS FOR SELECTIVE PRODUCTION OF HALOSILANES FROM SILICON-CONTAINING TERNARY INTERMETALLIC COMPOUNDS
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A process includes contacting an organohalide with a ternary intermetallic compound at a temperature of 300 °C to 700 °C to form a reaction product including a halosilane. The ternary intermetallic compound includes three metals. The first metal is Cu or Mg; the second metal is Au, Ni, or Pd; and the third metal is Si.
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-
Paragraph 0044
(2014/08/06)
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- Alternative methods for the synthesis of organosilicon compounds
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A method of forming chloro-substituted silanes from the reaction of an alkoxy-or acetoxy-substituted silane with a chlorinating agent in the optional presence of a catalyst is provided. For instance, chloro-substituted silanes, including but not limited to silicon tetrachloride, are formed by reacting a chlorinating agent, such as thionyl chloride, with an alkoxysilane having the formula (R'O)4-xSiRx, where R and R' are independently selected alkyl groups comprising one or more carbon atoms and x is 0, 1, 2, or 3. The catalyst may be dimethylformamide, (chloromethylene)dimethyliminium chloride, or triethylamine, among others. The chloro-substituted silane formed in the reaction along with several by-products has the formula (R'O)4-x-ySiRxCly; where x is 0, 1, 2, or 3 and y is 1, 2, 3, or 4. One of the by-products of the reaction is an alkyl chloride.
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Paragraph 0034; 0035; 0062-0064
(2013/09/26)
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- ALTERNATIVE METHODS FOR THE SYNTHESIS OF ORGANOSILICON COMPOUND
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A method of forming chloro-substituted silanes from the reaction of an alkoxysilane with a chlorinating agent in the optional presence of a catalyst is provided. More specifically, chloro-substituted silanes, including but not limited to silicon tetrachloride, are formed by reacting a chlorinating agent, such as thionyl chloride, with an alkylalkoxysilane having the formula (R'0)4-xSiRx, where R and R' are independently selected alkyl groups comprising one or more carbon atoms and x is 0, 1, 2, or 3. The catalyst may be dimethylformamide, (chloromethylene)dimethyliminium chloride, or triethylamine, among others. The chloro- substituted silane formed in the reaction along with several by-products has the formula (RO)4-x-ySiRxCly; where x is 0, 1, 2, or 3 and y is 1, 2, 3, or 4. One of the by-products of the reaction is an alkyl chloride.
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Paragraph 0062-0064
(2013/09/26)
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- Thermal restructuring of silica-grafted TiClx species and consequences for epoxidation catalysis
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TiCl4 grafted to dehydrated silica is an industrially applied catalyst for the epoxidation of propylene. As with many heterogeneous catalysts, the precise nature of the surface species is not yet fully known, prohibiting reliable structure-activity correlations. In this study, the speciation and restructuring of site-isolated TiIV Lewis acid centers was carefully investigated by using a variety of techniques. The initially formed SiOTiCl 3 species were found to restructure upon heating through the transfer of Cl ligands to the silica surface, eventually leading to tripodal (SiO) 3TiCl species. The superior activity and stability of such tripodal species is demonstrated for catalytic olefin epoxidation under continuous flow conditions. Anchoring titanium: Grafting of TiCl4 to site-isolated silanol groups on silica initially leads to freely rotating species. Upon heating, a thermal restructuring takes place, causing the elimination of TiCl4 and the formation of more strongly anchored titanium species, which were found to be highly active and stable epoxidation catalysts (see figure). Copyright
- Mania, Philipp,Verel, Rene,Jenny, Florian,Hammond, Ceri,Hermans, Ive
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p. 9849 - 9858
(2013/08/23)
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- Reaction of vanadocene and vanadocene dichloride with ortho-iodobenzoic acid
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At the interaction of bis (η5-cyclopentadienyl)vanadium with iodobenzoic acid or trimethylsilyl o-iodobenzoate in toluene depending on the ratio of the initial reagents bis(η5-cyclopentadienyl)vanadium(o- iodobenzoate) or η5/su
- Gordetsov,Zimina,Ur'Yash,Moseeva
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p. 299 - 302
(2013/08/15)
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- Catalytic disproportionation of methyltrichlorosilane by AL-MCM-41 to prepare dichlorodimethylsilane
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Al-MCM-41 samples with various Si/Al ratios were prepared and then used to disproportionate methyltrichlorosilane (MTS) to produce dichlorodimethylsilane (DMCS). The catalysts were characterized by FT-IR, X-ray powder diffraction (XRD), 27Al magic angle spinning nuclear magnetic resonance ( 27Al MAS NMR), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N2 absorption-desorption. It reveals that all samples show the hexagonal structure of MCM-41 and exhibit large BET surface areas (over 842m2g1). FT-IR spectra of pyridine adsorption demonstrates that Al-MCM-41 samples have Lewis (L) and Brnsted (B) acidic sites, and the B acidic sites are stable in the temperature ranging from 423 to 623K. The effects of aluminum content and temperature on the disproportionation reaction were also investigated. The results show that the Al-MCM-41 with the Si/Al ratio of 15:1 exhibits an excellent activity with 100% conversion of MTS and 47% selectivity of DMCS at 623K under atmospheric pressure. Taylor and Francis Group, LLC.
- Fu, Qiong,Zhang, Ning,Zhang, Jun,Hong, Sanguo
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experimental part
p. 1183 - 1194
(2012/10/18)
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- Bis(3,5-dimethylpyrazol-1-yl)acetate bound to titania and complexed to molybdenum dioxido as a bidentate N,N0-ligand. Direct comparison with a bipyridyl analog in a photocatalytic arylalkane oxidation by O2
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Bis(3,5-dimethylpyrazol-1-yl)acetate, well known as a tridentate N,N,O ligand, was bound to MoO2Cl2 in a bidentate N,N manner by anchoring covalently, at first, the ligand onto a titanium oxide surface, followed by its complexation with the molybdenum dioxo entity. It was fully characterized by 13CPMAS NMR and FT-IR spectroscopy. The tethered complex was directly compared with an analogous bipyridyl species in the catalytic ethylbenzene oxidation byO2 at room temperature, atmospheric pressure, and under visible light. The bis(pyrazol-1-yl) catalyst exhibited a significant initial higher oxygen atom transfer (OAT) capability, well in accord with its electron donating property. It was, unfortunately, hampered by a premature leaching phenomenon, totally absent in the comparable bipyridyl system. Springer Science+Business Media B.V. 2012.
- Castellanos, Nelson J.,Martinez, Fernando,Paez-Mozo, Edgar A.,Ziarelli, Fabio,Arzoumanian, Henri
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p. 629 - 637
(2013/01/15)
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- IONIC COMPOUND, PROCESS FOR PRODUCING SAME, AND ION-CONDUCTIVE MATERIAL COMPRISING SAME
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The present invention provides a method of producing a tetracyanoborate-containing ionic compound in a milder condition more efficiently and less expensively than conventional methods, and a tetracyanoborate-containing ionic compound having a reduced content of impure components. An ionic compound of the present invention is represented by the following general formula (I), has a content of fluorine atom-containing impurities of 3 mol% or less per 100 mol% of the ionic compound, and a method for producing an ionic compound represented by the general formula (I) of the present invention comprises a step of reacting starting materials containing a cyanide and a boron compound. (In the formula, Ktm+ denotes an organic cation [Kt b]m+ or an inorganic cation [Kta]m+; and m denotes an integer of 1 to 3.)
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Page/Page column 41-42
(2011/06/23)
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- Scheme of hydrolysis of five-coordinate chlorosilanes by X-ray diffraction data
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Hydrolysis of monochelate five-coordinate chlorosilanes MeC(O)N(Me)CH 2SiMe2Cl (Ia), L7CH2SiMe 2Cl (Ib), L8CH2SiMe2Cl (Ic), PhtImCH2SiMe2Cl (Id), MeC(O)N(Me)CH2SiMePhCl (IIa), and Im5CH2SiMePhCl (IIe), containing a monoanionic C,O-chelating ligand LCH2 [L is an amide, n-membered lactam (L n), imide (Imn), or phthalimide (PhtIm) residue]. The structures of the starting chlorides and their hydrolysis products were established by means of X-ray diffraction analysis. Based on experimental and published data, a general scheme of hydrolysis of mono-C,O-chelate chlorosilanes was suggested, including initial formation of silyloxonium chlorides III and subsequent formation of disiloxane dihydrochlorides IV. Pleiades Publishing, Ltd., 2011.
- Shipov,Kramarova,Murasheva,Korlyukov,Pogozhikh,Tarasenko,Negrebetskii,Yakovlev,Baukov, Yu. I.
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experimental part
p. 2428 - 2439
(2012/04/10)
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- Formation of silicon-carbon bonds by photochemical irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe
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Photochemical irradiation of an equimolar mixture of (η5 -C5H5)Fe(CO)2SiR3, FpSiR 3, and FpMe leads to the efficient formation of the silicon-carbon-coupled product R3SiMe, R3 = Me 3, Me2Ph, MePh2, Ph3, ClMe 2, Cl2Me, Cl3, Me2Ar (Ar = C 6H4-p-X, X = F, OMe, CF3, NMe2). Similar chemistry occurs with related germyl and stannyl complexes at slower rates, Si > Ge Sn. Substitution of an aryl hydrogen to form FpSiMe2C6H4-p-X has little effect on the rate of the reaction, whereas progressive substitution of methyl groups on silicon by Cl slows the process. Also, changing FpMe to FpCH2SiMe3 dramatically slows the reaction as does the use of (η5-C 5Me5)Fe(CO)2 derivatives. A mechanism involving the initial formation of the 16e intermediate (η5-C 5H5)Fe(CO)Me followed by oxidative addition of the Fe-Si bond accounts for the experimental results obtained.
- Fortier, Skye,Zhang, Yongqiang,Sharma, Hemant K.,Pannell, Keith H.
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experimental part
p. 1041 - 1044
(2010/04/25)
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- Crystal structures of the iso-thiocyanatoberyllates (Ph4P) 2[Be(NCS)4] and (Ph4P)4[{Be 2(NCS)4(Li-NCS)2}{Be2(NCS) 6(Li-H2N2C2S2)}]
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Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph4P) 2[Be2Cl1S], reacts with excess trimethylsilyWio-thiocyanate to give a mixture of colourless single crystals of (Ph4P)2 [Be(NCS)4] (1) and (Ph 4P)4[(Be2(NCS)4(μ-NCS) 2) (Be2(NCS)6(μ-H2N 2C2S2)}] (2), which can be separated by selection. Both complexes were characterized by X-ray diffraction. Compound 1 can be prepared without byproducts by treatment of (Ph4P) 2[BeCl4] with excess Me3SiNCS in dichloromethane solution, 1: Space group IA/a, Z= 4, lattice dimensions at 100(2) K: a = b= 1091, 2(1), c = 3937.1(3) pm, R1 = 0.0474, The [Be(NCS)4]2- ion of 1 forms tetragonally distorted tetrahedral anions with Be-N distances of 1684(2) pm and weak intermolecular S-S contacts along [100] and [010]. 2-4CH2Cl2: Space group Pl, Z=1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, = 95.08(1) °, γ= 94.52(1) °, R1= 0.103, Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be 2(NCS)4(μ-NCS)2}2-, the beryllium atoms are connected by (NCS)" bridging groups forming centrosymmetric eightmembered Be2(NCS)2 rings with distances Be-N of 168(1) pm and Be-S of 235.2(9) pm. The second anion [Be2(NCS) 6(μ-H2N2C2S2)} 2- consists of two (Be(NCS)3)- units, which, are linked by the nitrogen atoms of the unique dimeric cyc/o-addition product of HNCS with BeN distances of 179(1) pm.
- Neumueller, Bernhard,Dehnicke, Kurt
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experimental part
p. 1206 - 1211
(2011/01/09)
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- Silyl stabilized azanes: Reactions of mono- and dilithium bis(trimethylsilyl)hydrazide with dichloro- and tetrachlorostannane
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SnCl4 acts primarily as an oxidant and oxidizes monolithium bis(trimethylsilyl) hydrazide 1 to mainly bis(trimethylsilyl)amine, BSA and tris(trimethylsilyl)hydrazine, TrSH and itself get reduced to SnCl2. Similarly, reaction of SnCl
- Kataria,Mayer,Vasisht,Venugopalan
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experimental part
p. 2252 - 2257
(2009/10/23)
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- Structural chemistry of borazines
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The solid-state structure of (HN=BF)3 has been redetermined. It is characterised by a stacking of the molecules, similar to hexagonal boron nitride. In contrast, (F3CH2N=BF)3 shows no intermolecular interactions between the planar borazine rings. In (Cl 2BN=BCl)3, the Cl2B groups are almost perpendicularly oriented to the planar borazine ring and its B-Cl bonds are shorter than the Cl-B bonds to the ring boron atoms. Reactions of (Cl 2BN=BCl)3 with Me3SiNMe2 allows a successive Cl/Me2N exchange. Depending on the molar ratio, the compounds [Cl(Me2N)BN=BCl]3, [(Me2N) 2BN=BCl]3 and [(Me2N)2BN=BNMe 2]3 are obtained. The latter two react with CH 2Cl2 by B-N bond cleavage of one ring boron bonded Me 2N group with formation of an N-H bond. These molecules not only possess a strongly distorted BN hexagon with short B-NH bonds but also a nonplanar borazine ring. The nonplanarity of the borazine ring is even more pronounced in [Me3SiN=BCl]3. A planar borazine ring is observed for (MeN=BBr)3. Its molecules are ordered into stacks by translation with borazine planes 4.2 A apart from each other. Characteristic of the structure are close contacts between neighbouring bromine atoms. Due to the steric demand of pentafluorophenyl groups, the borazine ring of (F5C6N=BBr)3 forms no stacks because one of the three F5C6 rings stands almost perpendicular to the borazine plane while the other two are twisted by 70°. Aminolysis of (F 5C6N=BBr)3 yields (F5C 6N=BNH2)3 with NH2 groups that are coplanar with the borazine ring. The phenyl groups of (HN=BPh)3 are twisted by only 30-40° relative to the borazine ring. A threefold crystallographic axis stands perpendicular to the ring plane. The sixfold crystallographic axis of the unit cell generates a channel structure with an internal diameter of 4.5 A. The two isomeric borazines, (iPrN=BMe) 3 and (MeN=BiPr)3 are structurally rather similar although the first of these has longer B-N bonds due to the shorter N-C bonds. Moreover, the B-N-B and N-B-N bond angles are slightly different. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Anand, Benadir,Noeth, Heinrich,Schwenk-Kircher, Holger,Troll, Alexander
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experimental part
p. 3186 - 3199
(2009/02/07)
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- Process For Preparing Methylchlorosilanes
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The invention relates to a process for the direct synthesis of methylchlorosilanes by reaction of chloromethane with a contact composition comprising silicon and copper catalyst, wherein the concentration of oxygen in the chloromethane used is reduced by mixing a) chloromethane which contains oxygen, and b) chloromethane which contains a gaseous boron compound.
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Page/Page column 3
(2008/06/13)
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- Unmodified nano-powder magnetite catalyzes a four-component aza-Sakurai reaction
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A new catalyst for an old material: magnetite is an excellent Lewis acid catalyst for the four-component aza-Sakurai reaction. The process could be repeated up to 15-times without losing effectiveness, with the catalyst recycling being as easy as the use of a simple magnet. The catalyst is selective and could discriminate between aldehyde and ketone functionalities, catalyzing first the reaction with the higher electrophilic aldehyde.
- Martinez, Ricardo,Ramon, Diego J.,Yus, Miguel
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experimental part
p. 1235 - 1240
(2009/05/30)
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- On the reaction of hexachlorocyclotriphosphazene with heptamethyldisilazane. Crystal structure of P3N3Cl 5{N(CH3)[Si(CH3)3]}
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The reaction of P3N3Cl6 (1) with heptamethyldisilazane in the molar ratio 1:1 leads to the formation of 2,4,4,6,6-pentachloro-N-methyl-N-(trimethylsilyl)cyclotriphosphazen-2-amine, P3N3Cl5{N(CH3)[Si(CH 3)3]} (2). Compound 2 was characterized by elemental analysis and spectroscopically. Molecular and crystal structures of 2 were determined by X-ray diffraction. 2 is monoclinic, space group P21/n. Experimental data were compared with results of DFT calculations.
- Voznicova, Radka,Alberti, Milan,Taraba, Jan,Dastych, Dalibor,Kubacek, Pavel,Prihoda, Jiri
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p. 1407 - 1419
(2008/09/16)
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- Novel perfluoroalkanesulfonamide compounds
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The present invention provides compounds represented by the formula Y+?N(SO2Rf)(CF3). Such a compound can be manufactured through a reaction between M+?N(SO2Rf)(CF3) and Y+?B. The present invention also provides compounds represented by the formula Y+?N(SO2Rf)(CN). Such a compound can be manufactured through a reaction between M+?N(SO2Rf)(CN) and Y+?B. Rf in the above formulae is a perfluoroalkyl group. Y+ is an organic or inorganic cation. ?B is an organic or inorganic anion. M+ is an alkali metal cation or a silver cation.
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Page/Page column 23
(2008/06/13)
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- Catalytic cleavage of phosphate ester bonds by boron chelates
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Novel chemical compounds are disclosed having the general formula L{YXm}n, wherein X is selected from the Group 13 elements, Y is a halide, and L is a chelating ligand containing at least one binding atom contacting the Group 13 element, the atom being selected from the group consisting of C, N, O, and S, and m and n are integers having a value of at least 1. L may be a Schiff base type ligand, such as a salen ligand. The compositions of the present invention may be bidentate, quadridentate, or greater. The compositions may be used in dealkylation of phosphate esters or ethers. Advantageously, the methods of the present invention may be rendered catalytic.
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Page/Page column 5-7
(2008/06/13)
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- Highly efficient O-silylation of alcohol with vinylsilane using a Rh(l)/HCl catalyst at room temperature
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Highly efficient O-silylation of alcohol with vinylsilane was developed using a catalyst system consisting of [(COE)2RhCl]2 and HCl. In this reaction, a key intermediate is chlorosilane, generated from vinylsilane and HCl, which can be regenerated in the catalytic cycle. Various alcohols and vinylsilanes were applied to the preparation of silyl ether compounds with this catalyst system.
- Park, Jung-Woo,Jun, Chul-Ho
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p. 4073 - 4076
(2008/02/11)
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