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首页> 外文期刊>Chemistry: A European journal >A Comprehensive Theoretical Study on the Reactions of Sc~+ with C_nH_(2n+2) (n = 1-3): Structure, Mechanism, and Potential-Energy Surface
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A Comprehensive Theoretical Study on the Reactions of Sc~+ with C_nH_(2n+2) (n = 1-3): Structure, Mechanism, and Potential-Energy Surface

机译：Sc〜+与C_nH_（2n + 2）（n = 1-3）反应的综合理论研究：结构，机理和势能面

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The reactions of Sc~+(~3D) with methane, ethane, and propane in the gas phase were studied theoretically by density functional theory. The potential energy surfaces corresponding to [Sc, C_n, H_(2n+2)]~+ (n = 1-3) were examined in detail at the B3LYP/6-311 ++ G(3df, 3pd//B3LYP/6-311+G(d,p) level of theory. The performance of this theoretical method was calibrated with respect to the available thermochemical data. Calculations indicated that the reactions of Sc~+ with alkanes are multichannel processes which invovle two general mechanisms: an addition-elimination mechanism, which is in good agreement with general mechanism proposed from earlier experiments, and a concerted mechanism, which is presented for the first time in this work. The addition-elimination reactions are favorable at low energy, and the concernted reactions could be alternative pathways at high energy. In most cases, the energetic bottleneck in the addition-elimination mechanism is the initial C-C or C-H activation. The loss of CH_4 and/or C_2H_6 from Sc~+ + C_nH_(2n+2) (n = 2,3) can proceed along both the initial C-C activation branch and the C-H activation branch. The loss of H_2 from Sc~+ + C_nH_(2n+2) (n = 2,3) can proceed not only by 1,2-H_2 and/or 1,3-H_2 elimination, but also by 1,1-H_2 elimination. The reactivity of Sc~+ with alkanes is compared with those reported earlier for the reactions of the late first-row transition-metal ions with alkanes.
机译：用密度泛函理论研究了Sc〜+（〜3D）与甲烷，乙烷和丙烷在气相中的反应。在B3LYP / 6-311 ++ G（3df，3pd // B3LYP / 6）上详细检查了与[Sc，C_n，H_（2n + 2）]〜+（n = 1-3）对应的势能面-311 + G（d，p）的理论水平。该理论方法的性能已根据可用的热化学数据进行了校准。计算表明，Sc〜+与烷烃的反应是多通道过程，涉及两个普遍机理：与早期实验中提出的通用机理相吻合的加成消除机理，以及首次在本文中首次提出的协同机理，加成消除反应在低能下是有利的，所关注的反应可以是高能的替代途径。在大多数情况下，加成消除机制的高能瓶颈是CC或CH的初始活化。Sc〜+ + C_nH_（2n + 2）导致CH_4和/或C_2H_6的损失（n = 2,3）可以同时沿着初始CC激活分支和CH ac tivation分支。 Sc〜+ + C_nH_（2n + 2）（n = 2,3）导致的H_2的损失不仅可以通过1,2-H_2和/或1,3-H_2的消除来进行，还可以通过1,1-H_2的消除来进行消除。将Sc〜+与烷烃的反应性与较早报道的晚期第一行过渡金属离子与烷烃的反应进行了比较。

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