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Theoretical Study on the Mechanisms of Cu-catalyzed Cycloadditions and Fe-catalyzed Carbonylations

Author: WuHaiLing
Tutor: LiMing
School: Southwestern University
Course: Physical and chemical
Keywords: Copper-catalyzed Reaction Mechanism Density functional theory Iron-catalyzed
CLC: O643.32
Type: Master's thesis
Year: 2010
Downloads: 105
Quote: 1
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Abstract


In this paper, density functional theory were of copper catalyzed alkynyl ketone Diazoamides of [41] cycloaddition reaction of Fe (CO) 5 Fe 3 (CO) 12 catalyzed alkyne carbonylation reaction mechanism studies generated succinimide compounds. Each stationary structure fully optimized B3LYP functional reaction route cycle may be based on the system we designed two important transition states IRC scan to confirm its legitimacy. By comparing the reaction of the route in the activation energy of the transition states, we get the reaction of the advantage line, to determine the mechanism of the reaction, and the polarized continuum model (PCM) to consider the impact of the solvent on the energy of each species in the reaction. The 1 copper catalytic alkynyl ketone Diazoamides of cycloaddition reactions theoretical study using density functional theory B3LYP functional copper catalyzed alkynyl ketone and Diazoamides, [41] cycloaddition reaction theory research. The reaction system, the catalyst of the copper metal is first generated copper metal carbene intermediates, the relatively rapid reaction of this step, the release member of nitrogen. The resulting metal carbene missing electron-reactive intermediates, it is easy to accept electrons. Carbonyl oxygen and alkynyl groups can provide electronic Therefore, the copper metal carbene either with the carbonyl oxygen effect, can also be role and alkynyl group. Designed two possible reaction cycle diagram, calculation results show that in the gas phase or in a solvent metal carbene and the carbonyl oxygen role in this reaction path of lower energy, suggesting that this entry reaction path dominant , is the preferred reaction path. Carbene and the carbonyl oxygen after the carbene carbon atom attack the alkynyl end bit of carbon atoms, [41] cycloaddition reaction occurs. Finally, after a hydrogen transfer, off catalyst obtained polysubstituted furans. Occur the alkynyl ketone Diazoamides of the copper-catalyzed [41] cycloaddition reaction mainly by the following three parts: (1) the generation of copper carbene; (2), [41] cycloaddition reaction: ( 3), and proton transfer. In addition, the solvation effect significantly reduces the relative Gibbs free energy of the various species, the solvation effect of all structures are negative, and the reaction in the solvent ClCH 2 CH 2 Cl easier. The proposed mechanism is reasonable to explain all phenomena. 2 iron catalytic synthesis of succinimide compounds theoretical study using density functional theory B3LYP functional reaction of Fe (CO) 5 and Fe3 (CO) 12 catalyzed alkyne carbonyl groups generated succinimide compounds theoretical research. Designed respectively Fe (CO) 5 and Fe3 (CO) 12 as a catalyst for the reaction in the cycle diagram of the possible route through the analysis of the electronic effect of the various species in the reaction, steric, discloses the catalytic nature of the two catalysts. Of Fe (CO) 5 and Fe 3 (CO) 12 energy is seen as a catalyst for the catalytic reaction, two catalysts have similar catalytic nature , are ammonia First substituted carbonyl group and the catalyst with bits, and then alkynyl stars step carbonyl group of the catalyst complex, the hydrogen in the ammonia on the very easily leaving transferred to a carbonyl oxygen atom, through a hydrogen transfer transition state. The nitrogen atoms offensive carbonyl oxygen atom to generate CN key ring closure. Among them, the highest activation energy of the hydrogen transfer reaction rate-controlling step. The results show that, with Fe 3 (CO) 12 as the catalytic effect better. In addition, in the solvent THF, and the reaction intermediates and transition states of the energy is greatly reduced, so that the reaction is more easily performed.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic > Catalytic reaction
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