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Mechanistic insights into the reaction between VO2+ and propene based on a DFT study

机译：基于DFT研究的VO2 +与丙烯反应机理的机械见解

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摘要

Calculations based on density functional theory have been carried out to investigate the free energy profiles at singlet and triplet electronic states associated with the gas-phase ion/molecule reactions of VO2++ ((1)A(1)/(3)A") with propene. The complex potential energy Surfaces, including Six reaction pathways (three dehydrogenation and three oxygen transfer processes), have been explored and analyzed. Along dehydrogenation reactive channels, three final products can be obtained: V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and allene (path Dehl), being the most kinetically and thermodynamically favorable reaction pathway, V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and propyne (path Deh2),and VO2+ ((1)A(1)/(3)A") and H-2 plus allene (path Deh3). The oxyoenation processes can yield its final products Vo(+) ((1)Delta/(3)Sigma) and acetone (path Ox1), VO+ ((1)Delta/(3)Sigma 2) and propanaldehyde (path Ox2), and VO+ ((1)Delta/(3)Sigma) and H-2 and propenaldehyde (path Ox3). Both paths Deh1 and Deh2 are associated with two consecutive hydrogen transfer processes from carbon atoms of the propene fragment to vanadyl oxygen atoms, while in path Deh3 the second hydrogen migration takes place to the vanadiurn atorn followed by the formation ola hydrogen molecule. Both paths Ox1 and Ox2 comprise an intramolecular hydrogen transfer between the ethylenic moiety of the propene fragment, while two consecutive hydrogen transfer processes take place from the propene fragment to oxygen and vanadium atoms of the vanadyl moiety along path Ox3. Three crossing points between both electronic states take place along path Deh1 (CP-Deh1) and path Deh2 (CP-Deh2) and in the entrance channel of oxidation processes (CP-Ox). A comparison with previous works on related reactions VO2+ + C2H4, VO2 + C2H6, and VO2+ + C3H8 allows us to rationalize the different reactivity patterns.
机译：进行了基于密度泛函理论的计算，以研究与VO2 ++（（1）A（1）/（3）A“）的气相离子/分子反应相关的单重态和三重态电子态的自由能分布对包括六个反应路径（三个脱氢和三个氧转移过程）的复杂势能表面进行了研究和分析，沿着脱氢反应通道，可以获得三个最终产物：V（OH）（2）（+） （（1）Sigma（+）/（3）Sigma（-））和丙二烯（路径Dehl），是动力学和热力学上最有利的反应途径，V（OH）（2）（+）（（1）Sigma（ +）/（3）Sigma（-））和丙炔（路径Deh2），VO2 +（（1）A（1）/（3）A“）和H-2加烯键（路径Deh3）。氧合过程可产生其最终产物Vo（+）（（1）Delta /（3）Sigma）和丙酮（路径Ox1），VO +（（1）Delta /（3）Sigma 2）和丙醛（路径Ox2）， VO +（（1）Delta /（3）Sigma）和H-2和丙醛（路径Ox3）。路径Deh1和Deh2均与从丙烯片段的碳原子到钒氧原子的两个连续氢转移过程相关，而在路径Deh3中，第二个氢迁移发生在香草醛中，随后形成1a氢分子。路径Ox1和Ox2都包含丙烯片段的烯键部分之间的分子内氢转移，而沿着路径Ox3从丙烯片段到钒基部分的氧和钒原子发生了两个连续的氢转移过程。沿路径Deh1（CP-Deh1）和路径Deh2（CP-Deh2）以及氧化过程的入口通道（CP-Ox），在两个电子状态之间发生三个交叉点。与以前关于相关反应VO2 + + C2H4，VO2 + C2H6和VO2 + C3H8的研究进行比较，可以使我们合理化不同的反应模式。

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