A density functional theory study on the mechanism of the allylpalladium-catalyzed dehydrogenation of aldehydes and cyclic ketones

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Progress in Reaction Kinetics and Mechanism Pub Date : 2021-01-01 DOI:10.1177/14686783211020600
Anan Haj Ichia Arisha
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Abstract

The results of density functional theory calculations at the APFD/SDD level are detailed herein in order to study the main steps in the α,β-dehydrogenation of aldehydes and cyclic ketones in the presence of an allylpalladium complex catalyst. The mechanism is believed to proceed via an allylpalladium enolate complex (A) in equilibrium with the carbon-bonded complex (B), followed by β-hydride elimination to yield the allylpalladium hydride coordinated to the α,β-unsaturated carbonyl (complex C). The optimized structures and detailed energy profiles of these intermediates and their corresponding transition states are presented herein. The results indicate that the intermediates and their transition states are more stable in THF solution than in the gas phase. In detail, the energy barriers for the two steps are found to be 25.22 and 11.13 kcal/mol, respectively, in THF, and 29.93 and 9.77 kcal/mol, respectively, in the gas phase.
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烯丙基钯催化醛和环酮脱氢反应机理的密度泛函理论研究
本文详细介绍了密度泛函理论在APFD/SDD水平上的计算结果,以研究烯丙基钯配合物催化剂存在下醛和环酮的α,β-脱氢的主要步骤。该反应机理是通过烯丙基钯烯酸酯配合物(A)与碳键配合物(B)平衡,然后通过β-氢化物消除生成与α,β-不饱和羰基(C)配位的烯丙基钯氢化物。本文给出了这些中间体的优化结构和详细的能量分布及其相应的过渡态。结果表明,中间产物及其过渡态在四氢呋喃溶液中比在气相中更稳定。在THF中,这两步反应的能垒分别为25.22和11.13 kcal/mol;在气相中,这两步反应的能垒分别为29.93和9.77 kcal/mol。
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来源期刊
CiteScore
2.10
自引率
0.00%
发文量
5
审稿时长
2.3 months
期刊介绍: The journal covers the fields of kinetics and mechanisms of chemical processes in the gas phase and solution of both simple and complex systems.
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