18296-01-0

Upstream product

• 617-86-7 triethylsilane 
• 124-38-9 carbon dioxide 
• 74-85-1 ethene 

Downstream Products

• 1112-48-7 triethyl-bromo-silane 
• 358-43-0 triethylsilyl fluoride 
• 590-29-4 potassium formate 
• 64-18-6 formic acid 
• 597-52-4 Triethylsilanol 
• 6343-54-0 N-benzylformamide 
• 766-93-8 N-cyclohexylformamide 
• 53798-89-3 N-sec-butylformamide 
• 994-49-0 hexaethyl disiloxane 
• 5464-77-7 N,N-dibenzylformamide 
• 1478224-51-9 C₂₁H₂₉NO₂Si 
• 3760-54-1 1-pyrrolidinecarboxaldehyde 
• 1478224-53-1 C₁₁H₂₃NO₂Si 
• 107-31-3 Methyl formate 

Relevant academic research and scientific papers

Deoxygenative reduction of carbon dioxide to methane, toluene, and diphenylmethane with [Et2Al]+ as catalyst

The strong Lewis acid [Et2Al]+ catalyzes the reduction of carbon dioxide with hydrosilanes under mild conditions to methane. In benzene solution, the side products toluene and diphenylmethane are also obtained through Lewis acid catalyzed benzene alkylation by reaction intermediates. Copyright

Catalytic CO2 hydrosilylation with [Mn(CO)5Br] under mild reaction conditions

Carbon dioxide hydrosilylation with earth-abundant transition-metal catalysts is an attractive alternative for the design of greener and cost-effective synthetic strategies. Herein, simple [Mn(CO)5Br] is an efficient precatalyst in the hydrosilylation of carbon dioxide with Et3SiH under mild reaction conditions. Using THF as a solvent, triethylsilylformate Et3SiCH(O)O was obtained in 67% yield after 1 h at 50 °C and 4 bar of CO2 pressure. The selectivity of the reaction was tuned by changing the solvent to a mixture of THF and toluene producing bis(triethylsilyl)acetal (Et3SiO)2CH2 in 86% yield. The CO2 hydrosilylation was also effective at room temperature and atmospheric pressure using either THF or the mixture THF/toluene as the solvent resulting in high Et3SiH conversion (92%–99%) but with a decrease in the selectivity. Radical trapping experiments indicated the participation of radical species in the catalytic mechanism. To the best of our knowledge, this is the first report on CO2 hydrosilylation catalyzed by transition-metal radical intermediates.

Catalytic reduction of CO2with organo-silanes using [Ru3(CO)12]

The reaction of carbon dioxide with Et3SiH in the presence of catalytic amounts of [Ru3(CO)12] as a catalytic precursor was achieved to produce silyl formate (Et3SiOCOH) 1s with a TON of 9000. A similar reaction in the presence of KF yielded potassium formate (8s) in a one-pot protocol with high selectivity using water or MeCN as the solvent. In the current report the complete reduction of carbon dioxide to methane was achieved, with the use of a more reactive silane (phenylsilane). A catalytically relevant species was the ruthenium cluster [H4Ru4(CO)12]. This is the second report on the hydrosilylation of carbon dioxide catalyzed by highly active and readily available ruthenium clusters and this is the first report of hydrosilylation of CO2to methane.

Ruthenium-Catalyzed Coupling Reactions of CO2 with C2H4 and Hydrosilanes towards Silyl Esters

A series of in situ-prepared catalytic systems incorporating RuII precursors and bidentate phosphine ligands has been probed in the reductive carboxylation of ethylene in the presence of triethylsilane as reductant. The catalytic production of propionate and acrylate silyl esters was evidenced by high-throughput screening (HTS) and implemented in batch reactor techniques. The most promising catalyst systems identified were made of Ru(H)(Cl)(CO)(PPh3)3 and 1,4-bis(dicyclohexylphosphino)butane (DCPB) or 1,1’-ferrocene-diyl-bis(cyclohexylphosphine) (DCPF). A marked influence of water on the acrylate/propionate selectivity was noted. Turnover numbers [mol mol(Ru)?1] up to 16 for acrylate and up to 68 for propionate were reached under relatively mild conditions (20 bar, 100 °C, 0.5 mol % Ru, 40 mol % H2O vs. HSiEt3). Possible mechanisms are discussed.

Iron Catalyzed CO2 Activation with Organosilanes

Abstract: Iron nanoparticles generated in situ from [Fe3(CO)12] catalyzed CO2 reduction in the presence of Et3SiH as a reductant and tetrabutylammonium fluoride as a promoter to yield silyl formate (1s) under relatively mild reaction conditions. Additionally, when CO2 hydrosilylation was carried out in water, the product of CO2 reduction was formic acid. Additionally, a similar reaction using [Fe3(CO)12] as a catalytic precursor, PhSiH3 as a reductant, and CO2 in the presence of amines allowed the immediate formation of ureas at room temperature. Here, CO2 acted as a C1 building block for value-added products.

Reductive transformation of CO2 with hydrosilanes catalyzed by simple fluoride and carbonate salts

Hydrosilylation of CO2 catalyzed by simple fluoride and carbonate salts, such as CsF and K2CO3, is described. Total yields up to 87% for the formylated product were achieved. Mechanistic investigations indicate the reaction proceeds via the formation of an active formate species. This catalytic system was also found to be applicable to formamide synthesis from amines, CO2, and hydrosilane.

Nickel-catalyzed hydrosilylation of CO2 in the Presence of Et3B for the synthesis of formic acid and related formates

The reaction of CO2 with Et3SiH catalyzed by the nickel complex [(dippe)Ni(μ-H)]2 (1) afforded the reduction products Et3SiOCH2OSiEt3 (12%), Et 3SiOCH3 (3%), and CO, which were characterized by standard spectroscopic methods. Part of the generated CO was found as the complex [(dippe)Ni(CO)]2 (2), which was characterized by single-crystal X-ray diffraction. When the same reaction was carried out in the presence of a Lewis acid, such as Et3B, the hydrosilylation of CO2 efficiently proceeded to give the silyl formate (Et3SiOC(O)H) in high yields (85-89%), at 80 C for 1 h. Further reactivity of the silyl formate to yield formic acid, formamides, and alkyl formates was also investigated.

Catalytic synthesis of silyl formates with 1 atm of CO2 and their utilization for synthesis of formyl compounds and formic acid

In the presence of simple Rh2(OAc)4 and K 2CO3, the hydrosilylation of CO2 (1 atm) with various hydrosilanes efficiently proceeded to afford the corresponding silyl formates in moderate to high yields (53-90% yields). By using the dimethylphenylsilyl formate produced by the hydrosilylation, formamides, formic acid, and a secondary alcohol (via an aldehyde) could be synthesized by the reaction with various nucleophilic reagents such as amines, aniline, water, and the Grignard reagent.