98272-26-5Relevant academic research and scientific papers
Hydrosilane σ-Adduct Intermediates in an Adaptive Zinc-Catalyzed Cross-dehydrocoupling of Si?H and O?H Bonds
Patnaik, Smita,Kanbur, Uddhav,Ellern, Arkady,Sadow, Aaron D.
supporting information, p. 10428 - 10436 (2021/05/27)
Three-coordinate PhBOX (Formula presented.) ZnR (PhBOX (Formula presented.) =phenyl-(4,4-dimethyl-oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 107) under solvent-free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono- to tri-alkoxylation, whereas tri-substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reactants. That is, the catalyst adapts its mechanism to access the most facile and efficient conversion. In particular, either alcohol or hydrosilane binds to the open coordination site on the PhBOX (Formula presented.) ZnOR catalyst to form a PhBOX (Formula presented.) ZnOR(HOR) complex under one set of conditions or an unprecedented σ-adduct PhBOX (Formula presented.) ZnOR(H?SiR′3) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ-bond metathesis reactions involving four-centered electrocyclic 2σ–2σ transition states are preceded by σ-adducts.
Endogenous X-C=O species enable catalyst-free formylation prerequisite for CO2reductive upgrading
Dai, Wenshuai,Li, Hu,Saravanamurugan, Shunmugavel,Wu, Hongguo,Yang, Song
supporting information, p. 5822 - 5832 (2020/10/21)
CO2, the main component of greenhouse gas, is currently developed as a promising surrogate of carbon feedstock. Among various conversion routes, CO2undergoing catalytic reduction can furnish hydrogen/energy carriers and value-added chemicals, while specific metal-containing catalysts or organocatalysts are often prerequisite for smooth proceeding of the involved reaction processes. In this work, both formic acid and N-containing benzoheterocyclic compounds (including various benzimidazoles, benzothiazole, and benzoxazole) along with silanols could be synthesized with high yields (>90%) from catalyst-free reductive upgrading of CO2under mild conditions (50 °C). The endogenous X-CO species, derived from the N-methyl-substituted amide-based solvent [Me2N-C(O)-R], especially PolarClean, and O-formyl group [O-C(O)-H] of in situ formed silyl formate, were found to play a prominent promotional role in the activation of the used hydrosilane for reductive CO2insertion, as demonstrated by density functional theory (DFT) calculations and isotopic labeling experiments. Moreover, reaction mechanisms and condition-based sensitivity assessment were also delineated.
Carbon Dioxide Reduction to Methanol Catalyzed by Mn(I) PNP Pincer Complexes under Mild Reaction Conditions
Bertini, Federica,Glatz, Mathias,St?ger, Berthold,Peruzzini, Maurizio,Veiros, Luis F.,Kirchner, Karl,Gonsalvi, Luca
, p. 632 - 639 (2019/01/08)
Well-defined Mn(I) hydrido carbonyl PNP pincer-type complexes were tested as efficient and selective nonprecious transition metal catalysts for the reduction of CO2 to MeOH in the presence of hydrosilanes. The choice of reaction temperature and
Synthesis of nitrogen and sulfur co-doped hierarchical porous carbons and metal-free oxidative coupling of silanes with alcohols
Chen, Bingfeng,Li, Fengbo,Mei, Qingqing,Yang, Youdi,Liu, Huizhen,Yuan, Guoqing,Han, Buxing
supporting information, p. 13019 - 13022 (2017/12/15)
Hierarchically porous N and S co-doped carbon was prepared by using 2,5-dihydroxy-1,4-benzoquinone as the carbon source, thiourea as the N and S source, and SiO2 particles as the template. Using the material as the catalyst, oxidative coupling of silanes with alcohols was conducted for the first time under metal-free conditions.
