<scp>M</scp>üller–<scp>R</scp>ochow Synthesis: The Direct Process to Methylchlorosilanes

Kalchauer, Wilfried; Pachaly, Bernd

doi:10.1002/9783527610044.hetcat0134

Cited by 29 publications

(19 citation statements)

References 35 publications

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“…Some of these precursors, like MeSiCl 2 H, are conveniently obtained as byproducts of the Müller–Rochow process. In contrast, Me 2 SiClH synthesis suffers from low crude yields (0.01–0.5%, Scheme a) and challenging separation procedures, necessitating alternative synthetic routes to hydro(chloro)silanes from chlorosilanes . Hydrosilanes can be prepared by salt metathesis from chlorosilanes with LiAlH 4 (Scheme b).…”

Section: Introductionmentioning

confidence: 99%

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

et al. 2018

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Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OTf -) Me3-nSiX1+n (X = Cl, OTf; n = 0, 1) to hydrosilanes at mild conditions (4 bar H2, room temperature) is reported using low loadings (1 mol-%) of the bifunctional catalyst [Ru(H)2CO(HPNP iPr )] (HPNP iPr = HN(CH2CH2P(iPr)2)2). Endergonic chlorosilane hydrogenolysis can be driven by chloride removal, e.g. with NaBAr F 4 (BAr F 4 -= B(C6H3-3,5-(CF3)2 -). Alternatively, conversion to silyl triflates enables facile hydrogenolysis with NEt3 as base, giving Me3SiH, Me2SiH2 and Me2SiHOTf, respectively, in high yields. An outer-sphere mechanism for silyl triflate hydrogenolysis is supported by DFT computations. These protocols provide key steps for the synthesis of the valuable hydrochlorosilane Me2SiClH, which can also be directly obtained in yields over 50% by hydrogenolysis of chlorosilane/silyl triflate mixtures. catalyzed hydrogenolysis of chlorosilanes and silyl triflates with low catalyst loadings.

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Section: Introductionmentioning

confidence: 99%

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

et al. 2018

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“…Polyborosiloxanes (PBSs) represent an important branch of polydimethylsiloxane (PDMS) derivatives. PBSs have attracted considerable industrial and academic interests over the past few years due to their thermodynamically stable backbone, which have been widely used as the components for self-adhering heat-stable and flame-retardant materials, , high-temperature resistance adhesives and coatings, − and as precursors for high-temperature stability and chemical resistance fibers and ceramics. − Abundant borono (Si–O–B(OH) 2 ) end groups of PBSs allow formation of reversible physical cross-links through hydrogen-bonding . Therefore, PBSs exhibit a viscous fluid behavior under long time scales and a rigid mechanical behavior under a rapid extensional strain.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Structure-Controlled Polyborosiloxanes and Investigation on Their Viscoelastic Response to Molecular Mass of Polydimethylsiloxane Triggered by Both Chemical and Physical Interactions

Tang

Wang

et al. 2016

Ind. Eng. Chem. Res.

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A series of polyborosiloxanes (PBSs) was synthesized by mixing hydroxy-terminated polydimethylsiloxanes (PDMS) and boric acid (BA) in toluene at 120 °C. The molecular masses of selected PDMS precursors were in a wide range, covering from below up to far above the critical entanglement molecular mass of PDMS. The reaction kinetics was followed by using Fourier transform infrared (FTIR) spectroscopy. Unreacted BA was removed from raw PBSs after the reactions. The influence of molecular mass of PDMS precursors on the rheological property of PBSs was explored by dynamic oscillatory frequency sweeps. The results showed that the plateau elastic moduli of PBSs were highly dependent on the molecular mass of PDMS precursors. The plateau elastic moduli of PBSs decreased at first and then increased with increasing molecular mass of PDMS precursors. PBS1 and PBS2 prepared from unentangled PDMS precursors showed sufficient fits by using the two-mode Maxwell model, whereas PBS3 to PBS6 prepared from highly entangled PDMS precursors showed obvious deviations from the two-mode Maxwell model. It could be concluded that the changing trend of plateau elastic modulus of PBSs versus molecular mass of PDMS precursors was determined by the number density of supramolecular interactions (Si−O:B weak bonding and hydrogen-bonding of the end groups Si−O−B(OH) 2 ) and the number density of topological entanglements.

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“…[3,4,5,6,7,8,9] Very few is known about the nature of boron compounds, which might be associated with industrial processes based on metallurgical grade silicon like the Siemens-Process or Müller-Rochow-Synthesis. [10] In one case an unknown boron containing compound has been reported in the boron quantification of acid digests of metallurgical grade silicon by inductively coupled plasma -optical emission spectroscopy. [11] Hence, in industrial processes for purification of chlorosilanes, [12] one of the key challenges is to remove contaminations by dopants (esp.…”

Section: Introductionmentioning

confidence: 99%

Unexpected Formation of the Highly Symmetric Borate Ion [B(SiCl₃)₄]⁻

Bochmann¹,

Böhme

Brendler

et al. 2021

Eur J Inorg Chem

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Disproportionation reactions of chlorosilane compounds in the presence of boron trichloride yield the compound H[B(SiCl 3 ) 4 ]. Spectroscopic analyses of the yellow-whitish solid with IR-, Raman-, and NMR-spectroscopy ( 29 Si, 11 B) show the presence of a highly symmetric anion containing boron, which is fourfold coordinated with silicon. Due to the high symmetry 1 J( 11 B, 29 Si) and even 1 J ( 10 B, 29 Si) couplings can be observed in the NMR spectra of the dissolved compound. The crystal structure analysis with a crystal obtained from toluene solution proves the existence of a highly symmetric borate anion, which is stabilized by four trichlorosilyl groups. The molecular structure consists of a para-protonated toluene cation and the weakly coordinating borate anion [B(SiCl 3 ) 4 ] À . Quantum chemical analysis of the tetrakis(trichlorosilyl)borate ion shows a negatively charged boron atom and the presence of polar SiÀ Cl and SiÀ B bonds. Highly reactive compounds [E(SiCl 3 ) n ] À which are stabilized solely by trichlorosilyl groups have been prepared with E=C, Si, Ge, P, S in recent years. The superacid H[B(SiCl 3 ) 4 ] represents a new member in this elusive compound family.

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Müller–Rochow Synthesis: The Direct Process to Methylchlorosilanes

Abstract: The sections in this article are Introduction Formation of Methylchlorosilanes Reaction Mechanism Copper Catalyst Promoters and Inhibitors Reactants and Raw Materials Influence of Temperature and Pressure Applications in the… Show more

Cited by 29 publications

References 35 publications

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Synthesis of Structure-Controlled Polyborosiloxanes and Investigation on Their Viscoelastic Response to Molecular Mass of Polydimethylsiloxane Triggered by Both Chemical and Physical Interactions

Unexpected Formation of the Highly Symmetric Borate Ion [B(SiCl₃)₄]⁻

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Müller–Rochow Synthesis: The Direct Process to Methylchlorosilanes

Abstract: The sections in this article are Introduction Formation of Methylchlorosilanes Reaction Mechanism Copper Catalyst Promoters and Inhibitors Reactants and Raw Materials Influence of Temperature and Pressure Applications in the… Show more

Cited by 29 publications

References 35 publications

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Synthesis of Structure-Controlled Polyborosiloxanes and Investigation on Their Viscoelastic Response to Molecular Mass of Polydimethylsiloxane Triggered by Both Chemical and Physical Interactions

Unexpected Formation of the Highly Symmetric Borate Ion [B(SiCl3)4]−

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Unexpected Formation of the Highly Symmetric Borate Ion [B(SiCl₃)₄]⁻