Direct Formation of Element Chlorides from the Corresponding Element Oxides through Microwave‐Assisted Carbohydrochlorination Reactions

Nordschild, Simon; Auner, Norbert

doi:10.1002/chem.200701670

Cited by 11 publications

(6 citation statements)

References 33 publications

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“…Tetrachlorosilane is easily available directly from SiO 2 ‐based materials by using a carbohydrochlorination reaction44 and as a byproduct in industrial large‐scale processes, such as the Rochow–Müller Direct Process for dimethyldichlorosilane production20c, 45 or the Siemens Process to produce photovoltaic and/or electronic grade silicon 17. Thus, SiCl 4 might become a promising candidate for silicon and silicone production in an experimentally simple technical process.…”

Section: Resultsmentioning

confidence: 99%

Amorphous Silicon: New Insights into an Old Material

Spomer

Holl

Zherlitsyna

et al. 2015

Chemistry A European J

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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 Men Si(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 Men Si(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.

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Section: Resultsmentioning

confidence: 99%

Amorphous Silicon: New Insights into an Old Material

Spomer

Holl

Zherlitsyna

et al. 2015

Chemistry A European J

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“…This idea was investigated by Nordschild and Auner, who investigated the carbochlorination of calcium phosphate, Ca 3 (PO 4 ) 2 , with hydrogen chloride and carbon under microwave conditions . Phosphorus(III) chloride was collected in a cold trap and identified by its 31 P NMR chemical shift.…”

Section: P(iii) Compounds As the Bottleneckmentioning

confidence: 99%

Let’s Make White Phosphorus Obsolete

Geeson

Cummins

2020

ACS Cent. Sci.

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Industrial and laboratory methods for incorporating phosphorus atoms into molecules within the framework of Green Chemistry are in their infancy. Current practice requires large inputs of energy, involves toxic intermediates, and generates substantial waste. Furthermore, a negligible fraction of phosphorus-containing waste is recycled which in turn contributes to negative environmental impacts, such as eutrophication. Methods that begin to address some of these drawbacks are reviewed, and some key opportunities to be realized by pursuing organophosphorus chemistry under the principles of Green Chemistry are highlighted. Methods used by nature, or in the chemistry of other elements such as silicon, are discussed as model processes for the future of phosphorus in chemical synthesis.

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“…Improvements in the methods for purifying phosphoric acid have been such that, nowadays, the purity of H 3 PO 4 produced by the wet process rivals that produced by the thermal process, allowing wet process phosphoric acid to be used in food-grade applications . The higher energy requirements of the thermal process, in addition to the toxicity and pyrophoric properties of P 4 , provide motivation for eliminating P 4 in favor of phosphoric acid as the key starting material for the production of P-containing chemicals. , Along these lines, a microwave-assisted preparation of PCl 3 from calcium phosphate in a scheme that is thought to bypass elemental P has also been reported …”

Section: Introductionmentioning

confidence: 99%

“…More recently, however, sustainable and less energy-intensive approaches for preparing trichlorosilane have been explored. One example, already practiced industrially, is the reaction of silicon(IV) chloride with hydrogen. , Silicon(IV) chloride is a waste product of the PV industry or can alternatively be prepared in a redox-neutral process that involves converting silicate-containing minerals to a tetraalkyl orthosilicate and subsequent chlorination to silicon(IV) chloride. , A method for producing silicon(IV) chloride from silica in a process that avoids elemental silicon entirely was described and patented in 2012. , Finally, new methods for preparing silicon from silica using electrochemical techniques are areas of active investigation . These recent developments in the field of sustainable silicon chemistry hold promise for the use of trichlorosilane as a reducing agent for other element oxides.…”

Section: Introductionmentioning

confidence: 99%

Orthophosphate and Sulfate Utilization for C–E (E = P, S) Bond Formation via Trichlorosilyl Phosphide and Sulfide Anions

et al. 2019

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Reduction of phosphoric acid (H3PO4) or tetra-n-butylammonium bisulfate ([TBA][HSO4]) with trichlorosilane leads to the formation of the bis(trichlorosilyl)phosphide ([P(SiCl3)2]−, 1) and trichlorosilylsulfide ([Cl3SiS]−, 2) anions, respectively. Balanced equations for the formation of the TBA salts of anions 1 and 2 were formulated based on the identification of hexachlorodisiloxane and hydrogen gas as byproducts arising from these reductive processes: i) [H2PO4]− + 10HSiCl3 → 1 + 4O(SiCl3)2 + 6H2 for P and ii) [HSO4]− + 9HSiCl3 → 2 + 4O(SiCl3)2 + 5H2 for S. Hydrogen gas was identified by its subsequent use to hydrogenate an alkene ((−)-terpinen-4-ol) using Crabtree’s catalyst ([(COD)Ir(py)(PCy3)][PF6], COD = 1,5-cyclooctadiene, py = pyridine, Cy = cyclohexyl). Phosphide 1 was generated in situ by the reaction of phosphoric acid and trichlorosilane and used to convert an alkyl chloride (1-chlorooctane) to the corresponding primary phosphine, which was isolated in 41% yield. Anion 1 was also prepared from [TBA][H2PO4] and isolated in 62% yield on a gram scale. Treatment of [TBA]1 with an excess of benzyl chloride leads to the formation of tetrabenzylphosphonium chloride, which was isolated in 61% yield. Sulfide 2 was used as a thionation reagent, converting benzophenone to thiobenzophenone in 62% yield. It also converted benzyl bromide to benzyl mercaptan in 55% yield. The TBA salt of trimetaphosphate ([TBA]3[P3O9]·2H2O), also a precursor to anion 1, was found to react with either trichlorosilane or silicon(IV) chloride to provide bis(trimetaphosphate)silicate, [TBA]2[Si(P3O9)2], characterized by NMR spectroscopy, X-ray crystallography, and elemental analysis. Trichlorosilane reduction of [TBA]2[Si(P3O9)2] also provided anion 1. The electronic structures of 1 and 2 were investigated using a suite of theoretical methods; the computational studies suggest that the trichlorosilyl ligand is a good π-acceptor and forms σ-bonds with a high degree of s character.

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Direct Formation of Element Chlorides from the Corresponding Element Oxides through Microwave‐Assisted Carbohydrochlorination Reactions

Cited by 11 publications

References 33 publications

Amorphous Silicon: New Insights into an Old Material

Amorphous Silicon: New Insights into an Old Material

Let’s Make White Phosphorus Obsolete

Orthophosphate and Sulfate Utilization for C–E (E = P, S) Bond Formation via Trichlorosilyl Phosphide and Sulfide Anions

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