925-94-0Relevant academic research and scientific papers
Lewis Base Promoted Reduction of CO2 with BH3NH3 into Boryl Formates: CO2 as a Carbon Source in Organic Synthesis Under Mild Conditions
Zhang, Bo,Du, Gaixia,Hang, Wei,Wang, Sheng,Xi, Chanjuan
supporting information, p. 1739 - 1743 (2018/04/24)
Lewis base promoted selective reduction of CO2 into boryl formates by using BH3NH3 as a reductant under mild conditions has been reported. The boryl formates, generated in situ, were shown to be reactive and versatile sources of formyl compounds to create new C–N, C–O, and C–C bonds. The reactivity of the boryl formates to yield formic acid, formamides, formates, secondary alcohols, and benzoheterocyclic rings was investigated.
Molecular Iridium Complexes in Metal-Organic Frameworks Catalyze CO2 Hydrogenation via Concerted Proton and Hydride Transfer
An, Bing,Zeng, Lingzhen,Jia, Mei,Li, Zhe,Lin, Zekai,Song, Yang,Zhou, Yang,Cheng, Jun,Wang, Cheng,Lin, Wenbin
supporting information, p. 17747 - 17750 (2017/12/15)
Molecular iridium catalysts immobilized in metal-organic frameworks (MOFs) were positioned in the condensing chamber of a Soxhlet extractor for efficient CO2 hydrogenation. Droplets of hot water seeped through the MOF catalyst to create dynamic gas/liquid interfaces which maximize the contact of CO2, H2, H2O, and the catalyst to achieve a high turnover frequency of 410 h-1 under atmospheric pressure and at 85 °C. H/D kinetic isotope effect measurements and density functional theory calculations revealed concerted proton-hydride transfer in the rate-determining step of CO2 hydrogenation, which was difficult to unravel in homogeneous reactions due to base-catalyzed H/D exchange.
Trapping formaldehyde in the homogeneous catalytic reduction of carbon dioxide
Bontemps, Sebastien,Sabo-Etienne, Sylviane
supporting information, p. 10253 - 10255 (2013/10/21)
Formaldehyde detectives: Evidence for the production of formaldehyde during a ruthenium-catalyzed CO2 reduction process, and for its involvement in the formation of the resulting C2 compound, is disclosed. Ultimately, formaldehyde can be recovered by methanol trapping. HBPin=pinacolborane. Copyright
Oxidative functionalization of methane in the presence of a homogeneous rhodium-copper-chloride catalytic system: Transformation of acetic and propionic acids as solvent components
Chepaikin,Bezruchenko,Menchikova,Moiseeva,Gekhman,Moiseev
scheme or table, p. 133 - 142 (2012/01/13)
The oxidative functionalization of methane (O2, CO, 95°C, Rh III/CuI, II/Cl- catalytic system) was studied in an aqueous acetic or propionic acid medium. It was shown that oxidative decarbonylation of carboxylic acids takes place along with methanol and methyl carboxylate formation.
Oxygen-independent decarbonylation of aldehydes by cyanobacterial aldehyde decarbonylase: A new reaction of diiron enzymes
Das, Debasis,Eser, Bekir E.,Han, Jaehong,Sciore, Aaron,Marsh, E. Neil G.
supporting information; experimental part, p. 7148 - 7152 (2011/09/30)
Just add water: Structurally, cyanobacterial aldehyde decarbonylases are members of the non-heme diiron oxygenase family of enzymes. However, the enzyme catalyzes the hydrolysis of aliphatic aldehydes to alkanes and formate (see scheme), in an oxygen-independent reaction. This unusual and chemically difficult reaction most likely involves free radical intermediates. Copyright
Homogeneous catalytic oxidation of light alkanes: C-C bond cleavage under mild conditions
Chepaikin,Bezruchenko,Menchikova,Moiseeva,Gekhman
body text, p. 666 - 671 (2011/02/16)
The combined oxidation of CO and C2-C4 alkanes (associated petroleum gas and natural gas components) under the action of oxygen in trifluoroacetic acid solutions in the presence of rhodium and copper chlorides was accompanied by the oxidative degradation of C-C bonds in a hydrocarbon chain with the formation of carbonyl compounds, alcohols, and esters. For butane and isobutane, the reaction path with C-C bond cleavage was predominant. The buildup curves of isobutane oxidation products (both with the retention and with the degradation of the chain) were S-shaped and characterized by the same induction period; they did not pass through a maximum. A reaction scheme was proposed to reflect the main special features of the mechanism of transformations occurring in the O2/Rh/Cu/Cl- oxidation system.
Oxidation and Oxidative Carbonylation of Methane and Ethane by Hexaoxo-μ-peroxodisulfate(2-) Ion in Aqueous Medium. A Model for Alkane Oxidation through the Hydrogen-atom Abstraction Pathway
Lin, Minren,Sen, Ayusman
, p. 892 - 893 (2007/10/02)
In aqueous medium, at 105-115 deg C, SO4 radical-anion (generated from S2O82-) was found to abstract a hydrogen atom from methane and ethane to form the corresponding alkyl radicals which could be trapped efficiently by carbon monoxide, the resultant acyl radicals being ultimately converted into the homologous carboxylic acids.
CH3OCH.+, a New Stable C2H4O.+ Isomer, and a Reassessment of the Oxirane.+ Potential Surface
Buschek, J. M.,Holmes, J. L.,Terlouw, J. K.
, p. 7321 - 7325 (2007/10/02)
The .+ isomer of structure .+ has been shown to be unambiguously generated by CO2 loss from ionized methyl glyoxylate. ΔHf0 for this new ion was measured to be 224 +/- 1 kcal mol-1.The .+ ion produced by the loss of CH2O from ionized 1,3-dioxolane and by the loss of HCOOH from ionized methoxymethyl formate was proposed to have the structure .+, ΔHf0 = 206 +/- 2 kcal mol-1.Ionized oxirane in either its 2B1 or 2A1 state was proposed to be generated by loss of CO2 from ionized ethylene carbonate at a threshold energy corresponding to a ΔHf0 = 235 +/- 1 kcal mol-1.The structure assignments were aided by observations of collisional activation and metastable ion mass spectra.The common fragmentations of .+ and .+ ions, loss of CH3. and H., take place at similar high internal energies, leading to large kinetic energy releases in the metastable ion decompositions.Interpretations of the observations were in keeping with recent high-level ab initio molecular orbital theory calculations, but detailed mechanisms could not be established.
Equilibrium Deuterium Isotope Effects in Formic Acid-Hydrogen Exchange
Dave, S. M.,Ghosh, S. K.,Sadhukhan, H. K.
, p. 460 - 462 (2007/10/02)
Deuterium separation factors for formic acid-hydrogen exchange have been calculated as function of temperature and deuterium concentration in hydrogen, using the spectroscopic data.From the temperature dependence of the separation factors, the enthalpy of isotopic exchange reaction has been calculated.
