694-53-1Relevant articles and documents
Reversible Silylene Insertion Reactions into Si?H and P?H σ-Bonds at Room Temperature
Rodriguez, Ricardo,Contie, Yohan,Nougué, Raphael,Baceiredo, Antoine,Saffon-Merceron, Nathalie,Sotiropoulos, Jean-Marc,Kato, Tsuyoshi
, p. 14355 - 14358 (2016)
Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E?H σ-bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step.
Discrete spirobicyclic silicate anions with SiO2N2C, SiN2S2C and SiO4C frameworks
Narula, Suraj P.,Puri, Meenu,Garg, Neena,Puri, Jugal K.,Chadha, Raj K.
, p. 569 - 587 (2007)
Bis(2-aminobenzoato)phenylsilicate (1), bis(2-aminothiophenoxy) phenylsilicate (2), and bis(2-hydroxybenzoato) phenylsilicate (3) anions were obtained as their triethylammonium salts from the reactions of phenylsilane with appropriate ligands in the presence of triethylamine. The compounds were characterized by IR, multinuclear (1H, 13C, and 29Si) NMR, and FAB mass spectral data. Th X-ray crystal structure of 1.CH2Cl2 revealed slightly distorted trigonal bipyramidal geometry around silicon. The spirobicyclic silicate anions are the first examples with silicon-heteroatom linkages having six-membered (1) and five-membered (2) rings on silicon. Copyright Taylor & Francis Group, LLC.
SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
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Page/Page column 47, (2019/04/16)
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.
Electrochemical properties of arylsilanes
Biedermann, Judith,Wilkening, H. Martin R.,Uhlig, Frank,Hanzu, Ilie
, p. 13 - 18 (2019/03/27)
In the past, the electrochemical properties of organosilicon compounds were investigated for both fundamental reasons and synthesis purposes. Little is, however, known about the electrochemical behaviour of hydrogen-bearing arylsilanes. Here, we throw light on the electrochemical properties of 11 arylsilanes compounds, 2 of them synthesized for the first time. The oxidation potentials are found to depend on both the nature and number of the aryl groups. Based on these findings it was possible to establish some variation trends that match the expected structure–property correlations. Furthermore, we present first insights into the electrochemical reaction kinetics behind and identify several soluble electrochemical oxidation products.
CO Displacement in an Oxidative Addition of Primary Silanes to Rhodium(I)
Biswas, Abhranil,Ellern, Arkady,Sadow, Aaron D.
, (2019/03/11)
The rhodium dicarbonyl {PhB(Ox Me2)2ImMes}Rh(CO)2 (1) and primary silanes react by oxidative addition of a nonpolar Si-H bond and, uniquely, a thermal dissociation of CO. These reactions are reversible, and kinetic measurements model the approach to equilibrium. Thus, 1 and RSiH3 react by oxidative addition at room temperature in the dark, even in CO-Saturated solutions. The oxidative addition reaction is first-Order in both 1 and RSiH3, with rate constants for oxidative addition of PhSiH3 and PhSiD3 revealing kH/kD a 1. The reverse reaction, reductive elimination of Si-H from {PhB(Ox Me2)2ImMes}RhH(SiH2R)CO (2), is also first-Order in [2] and depends on [CO]. The equilibrium concentrations, determined over a 30 °C temperature range, provide ?"H° = a'5.5 ± 0.2 kcal/mol and ?"S° = a'16 ± 1 cal·mol-1K-1 (for 1 a?., 2). The rate laws and activation parameters for oxidative addition (?"Ha§§ = 11 ± 1 kcal·mol-1 and ?"Sa§§ = a'26 ± 3 cal·mol-1·K-1) and reductive elimination (?"Ha§§ = 17 ± 1 kcal·mol-1 and ?"Sa§§ = a'10 ± 3 cal·mol-1K-1), particularly the negative activation entropy for both forward and reverse reactions, suggest the transition state of the rate-Determining step contains {PhB(Ox Me2)2ImMes}Rh(CO)2 and RSiH3. Comparison of a series of primary silanes reveals that oxidative addition of arylsilanes is ca. 5× faster than alkylsilanes, whereas reductive elimination of Rh-Si/Rh-H from alkylsilyl and arylsilyl rhodium(III) occurs with similar rate constants. Thus, the equilibrium constant Ke for oxidative addition of arylsilanes is >1, whereas reductive elimination is favored for alkylsilanes.
Activations of all Bonds to Silicon (Si-H, Si-C) in a Silane with Extrusion of [CoSiCo] Silicide Cores
Handford, Rex C.,Smith, Patrick W.,Tilley, T. Don
supporting information, p. 8769 - 8772 (2019/06/07)
The [BP3iPr]Co(I) synthon Na(THF)6{[BP3iPr]CoI} (1, [BP3iPr] = κ3-PhB(CH2PiPr2)3-) reacts with PhSiH3 or SiH4 to form unusual {[BP2iPr](SiH2R)CoH2}=Si={H2Co[BP3iPr]} species (R = Ph, 2a; R = H, 2b; [BP2iPr] = κ2-PhB(CH2PiPr2)2) that result from activation of all Si - H and Si - C bonds in the starting silanes. Solution-spectroscopic data (multinuclear NMR, IR) for 2a,b, and the solid-state structure of 2a, indicate substantial Co=Si=Co multiple bonding and minimal interaction of the core Si atom with nearby hydride ligands. In the presence of 4-dimethylaminopyridine (DMAP), 1 reacts with PhSiH3 to give [BP3iPr](H)2CoSiHPh(DMAP) (3). Complexes 2a,b eliminate RSiH3 upon thermolysis in the presence of DMAP to generate {[BP2iPr]Co(NC5H3NMe2)}=Si={H2Co[BP3iPr]} (4).
Catalytic Reduction of Alkoxysilanes with Borane Using a Metallocene-Type Yttrium Complex
Aoyagi, Keiya,Matsumoto, Kazuhiro,Shimada, Shigeru,Sato, Kazuhiko,Nakajima, Yumiko
supporting information, p. 210 - 212 (2019/02/01)
The catalytic reduction of alkoxysilanes with the borane HBpin (pin = pinacolato) was achieved using a metallocene-type yttrium complex as a catalyst precursor. Mechanistic study supported the pivotal role of the rigid metallocene structure of the catalyst, which bears two bulky n5-C5Me4SiMe3 ligands, in suppressing the coordination of the side product MeOBpin that is generated during the reaction.
Synthesis of hydrosilanes: Via Lewis-base-catalysed reduction of alkoxy silanes with NaBH4
Aoyagi, Keiya,Ohmori, Yu,Inomata, Koya,Matsumoto, Kazuhiro,Shimada, Shigeru,Sato, Kazuhiko,Nakajima, Yumiko
supporting information, p. 5859 - 5862 (2019/05/27)
Hydrosilanes were synthesized by reduction of alkoxy silanes with BH3 in the presence of hexamethylphosphoric triamide (HMPA) as a Lewis-base catalyst. The reaction was also achieved using an inexpensive and easily handled hydride source NaBH4, which reacted with EtBr as a sacrificial reagent to form BH3in situ.
Custom Hydrosilane Synthesis Based on Monosilane
Yuan, Weiming,Smirnov, Polina,Oestreich, Martin
, p. 1443 - 1450 (2018/04/20)
The omnipresence of silicon compounds with carbon substituents in synthetic chemistry hides the fact that, except for certain substitution patterns at the silicon atom, their preparation is often far from trivial. The challenge is rooted in the lack of control over nucleophilic substitution with carbon nucleophiles at silicon atoms with three or four leaving groups. For example, SiCl4 usually converts into intractable mixtures of chlorosilanes, typically requiring several distillation cycles to reach high purity. Accordingly, there is no universal approach to silanes with heteroleptic substitution. Here, using a bench-stable SiH4 surrogate, we introduce a general strategy for the on-demand synthesis of silicon compounds decorated with different aryl and alkyl substituents. Reliable protocols are the basis of the selective and programmable synthesis of dihydro- and monohydrosilanes; aryl-substituted trihydrosilanes are also accessible in a straightforward fashion. These otherwise difficult-to-access hydrosilanes are only three or fewer easy synthetic operations away from the SiH4 surrogate. Synthesizing silicon compounds with different carbon substituents from inorganic silicon precursors, i.e., basic silicon chemicals with hydrogen, halogen, or alkoxy substitution, is an intricate and often insoluble task. It is generally difficult to chemoselectively address one of these groups in chemical reactions, particularly when two or more of those are identical. Complicated separation and purification procedures are the result. The challenge of making these silicon compounds containing silicon–carbon bonds, typically hydro- and chlorosilanes, is accentuated considering their high demand in academia and industry. The present approach is a step forward in solving those limitations. It hinges on the stepwise decoration of the silicon atom of a liquid monosilane surrogate. Further development of this strategy and adjusting it to industrial needs could pave the way to easy access of an even more diverse manifold of silicon compounds for synthetic chemistry and material science. Oestreich and colleagues present an approach to the chemoselective stepwise preparation of hydrosilanes with the general formula R4–nSiHn where n = 1–3 and R can be different aryl and alkyl groups. The starting point is a bench-stable SiH4 surrogate with two Si–H bonds masked as cyclohexa-2,5-dien-1-yl substituents. A sequence of palladium-catalyzed Si–H arylation and B(C6F5)3-promoted deprotection and transfer hydrosilylation enables the programmable synthesis of hydrosilanes, even with three different substituents at the silicon atom.
METHOD FOR PRODUCING HYDROSILANE
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Paragraph 0025, (2019/01/06)
PROBLEM TO BE SOLVED: To provide a method for producing hydrosilane capable of efficiently producing hydrosilane under mild conditions. SOLUTION: Provided is a method for producing hydrosilane where hydrosilane can be efficiently produced by reacting alkoxysilane having a structure represented by formula (a) with hydroborane and/or hydrogen under the presence of a complex with at least one kind of atom selected from the group consisting of a yttrium atom (Y), a zirconium atom (zr) and a hafnium atom (Hf) as a central metal(s)(in the formula (a), R denotes a 1 to 20C hydrocarbon group). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
