Search results for "Mechanism"

The Mechanism of Diene Polymerisation by Organolanthanide Catalysts Deduced from Microwave Experiments

2005

Isoprene polymerisation performed under microwave irradiation with [Nd(BH 4 ) 3 (THF) 3 ]/Mg(Bu) 2 and [Nd-(BH 4 ) 3 (THE) 3 ]/Al(Et) 3 showed an enhancement in reactivity, with selectivity being only slightly modified. An explanation of the observed effect is proposed based on our current knowledge of the catalytic mechanism and by considering the alkylated complex as an ion pair. An analogy is proposed with the pseudoanionic polymerisation of oxygenated monomers. Finally, depolymerisation is observed under microwave irradiation at high temperature.

Theoretical study of the mechanism of branching rearrangement of carbenium ions

1996

Abstract Owing to the practical interest of the acid catalyzed isomerization reactions of hydrocarbons, the mechanism of the branching rearrangements of C 4 H 9 + and C 5 H 11 + carbenium ions has been studied theoretically using ab initio methods which include electron correlation and extended basis sets. It has been found that the protonated cyclopropane-type species does not appear as a common intermediate for these reactions, since it is a transition state and not a minimum on the potential energy surfaces studied. In the case of C 4 H 9 + cation, the protonated methyl-cyclopropane ring is the transition state for the carbon scrambling reaction in the secondary n-butyl cation, while the…

Nickel-catalyzed carboxylation of aryl zinc reagent with CO2: A theoretical and experimental study

2019

Abstract Two Ni-complexes with 1,1′-bis(diphenylphosphino)ferrocene (dppf) and tricyclohexylphosphine (PCy3) ligands were tested for the Ni-catalyzed cross-coupling of aryl zinc reagent with CO2 to form aryl carboxylic acid. Theoretical study with the aid of density functional theory (DFT) was carried out to understand the detailed reaction mechanism. The reasonable reaction pathway was deduced. The simulation results suggested that the free energy barrier of the rate-limiting step with (dppf)Ni is only 1.64 kcal mol−1 higher than the barrier with (PCy3)2Ni. However, our experiment provided an unexpectedly low yield by using (dppf)Ni complex as the catalyst. Further theoretical study ascrib…

Hydro-dimerization of Pt2Cl2(C2H4)2: model reaction to capture details on catalytic mechanisms

2005

Abstract The density functional theory was employed to mimic the homogeneous hydro-dimerization of the Zeise-similar dichloro-bis(ethene)-platinum(II), PtCl 2 ( C 2 H 4 ) 2 . Three energy minima and four transition-states were involved in the reaction mechanism, which was even characterized by a catalytic cycle. The minima were fully optimized at B3LYP level whereas the transition-states were first individuated at the same level, by the synchronous transit-guided quasi-Newton method, then fully optimized. The mechanistic hypotheses on the PtCl 2 ( C 2 H 4 ) 2 dimerization implied the displacement of two ethene or two ethane molecules, respectively, occurring in absence or in presence of mol…

Structural dynamics in F1ATPase during the first reaction cycle of ATP hydrolysis

1991

Abstract The velocity of ATP hydrolysis, catalyzed by purified F 1 ATPase from Micrococcus luteus , was decelerated on decreasing the temperature. At 13′C one reaction cycle is completed after 20 s. Hydrolysis was triggered upon rapid mixing of the enzyme with ATP. During the first reaction cycle, succeeding structural alterations of the F 1 ATPase were traced by time resolved X-ray scattering. The scattering spectra obtained from consecutive intervals of 1 s, revealed the F 1 ATPase to pass a conformational state exhibiting an expanded (6%) molecular shape. The expanded state was observed between 45% and 65% of the time required to complete the reaction cycle. This pointx out a conformatio…

Residual Stresses and Reactivity of Solids. Determination and Part Plaid in the Reaction Mechanisms

1996

Kinetics of homogeneous catalytic chlorination of acetic acid

2007

The kinetics of the chlorination of acetic acid (HAc) to monochloroacetic acid (MCA) and the physical solubility of chlorine in HAc and its mixtures with MCA were investigated in a laboratory scale semibatch reactor. The temperature dependence of the Henry's constant was determined from solubility data obtained at temperatures between 70°C and 110°C. The kinetic experiments were performed at 75–100°C with 3–13 mol % acetyl chloride (AcCl) and 0–5 weight % H2SO4 added as catalysts. Gas chromatography was used to determine the concentrations of HAc, MCA, dichloroacetic acid and AcCl during the experiments. The results indicate that the reaction rate is independent of the concentrations of HAc…

Electrochemical Quartz Crystal Microbalance Study of Copper Electrochemical Reaction in Acid Medium Containing Chlorides

2006

Copper electrodissolution and electrodeposition were studied by means of gravimetric quartz crystal microbalance and electric cyclic voltammetry combined measurements. Relevant information on the mechanism of these electrochemical processes is provided by the analysis of experimental data and particularly of the mass change per charge unit. The copper electrodeposition and electrodissolution take place by means of two consecutive monoelectronic transfers where the anion participation in the reaction mechanism is specified. Besides, it is proved that the presence of molecular oxygen in the solution contributes to the formation of a passive layer on the surface of the metallic copper deposit.

Potassium demineralization of coconut fiber via combined hydrothermal treatment and washing: Effect on pyrolysis kinetics, mechanisms, and bio-oil co…

2021

Abstract Producing clean energy from waste biomass via pyrolysis is critical in reducing dependence on fossil fuels and alleviating their environmental impacts. Inherent potassium in low energy density coconut fibers reduces bio-oil yield and compromises bio-oil quality and the integrity of reactors within which pyrolysis occurs. The effect of consecutive hydrothermal treatment (180°C-220 °C) and water washing on coconut fiber demineralization, pyrolysis behavior, and bio-oil composition was investigated. Chemical fractionation method classified the most occurring inorganic (potassium) as ~76% water-soluble, ~19% ion-exchangeable, and ~5% acid-soluble species. Demineralization results show …

Catalytic Reaction Mechanism in Native and Mutant Catechol- O-methyltransferase from the Adaptive String Method and Mean Reaction Force Analysis.

2018

Catechol- O-methyltransferase is an enzyme that catalyzes the methylation reaction of dopamine by S-adenosylmethionine, increasing the reaction rate by almost 16 orders of magnitude compared to the reaction in aqueous solution. Here, we combine the recently introduced adaptive string method and the mean reaction force method, in combination with the structural and electronic descriptors to characterize the reaction mechanism. The catalytic effect of the enzyme is addressed by the comparison of the reaction in the human wild-type enzyme, in the less effective Y68A mutant, and in aqueous solution. The influence of these different environments at different stages of the chemical process and th…