Isomer-selected ion–molecule reactions of acetylene cations with propyne and allene
Isomer-selected ion–molecule reactions of acetylene cations with propyne and allene
复制标题
乙炔阳离子与丙炔和丙二烯的异构体选择离子分子反应
DOI：
10.1039/d0cp03953e
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发表时间：
2020
影响因子：
3.3
通讯作者：
Lewandowski, H. J.
中科院分区：
文献类型：
--
作者：
Schmid, P. C.;Greenberg, J.;Nguyen, T. L.;Thorpe, J. H.;Catani, K. J.;Krohn, O. A.;Miller, M. I.;Stanton, J. F.;Lewandowski, H. J.
化学的基本目标之一是确定分子结构如何影响相互作用并导致不同的反应产物。对异构体选择和分解的化学反应的研究可以直接阐明形式如何导致功能。在下文中，我们提出了乙炔阳离子（C2D2+）与C3H4的两种不同异构体之间的气相反应的结果：丙炔（DC3D3）和丙二烯（H2C3H2）。我们高度受控的离子捕获环境可以精确测定反应产物和动力学。从这些结果中，我们可以推断C2H2 ++ C3H4的潜在反应动力学的细节。通过实验结果和高层次的量子化学势能面计算的协同作用，我们能够确定两种异构体不同的反应机制。我们发现长程电荷交换没有复杂的形成是有利的丙二烯，而电荷交换导致一个中间反应复杂的丙炔，因此，不同的产品。因此，该反应显示出明显的异构体选择性双分子反应过程。
One of the fundamental goals of chemistry is to determine how molecular structure influences interactions and leads to different reaction products. Studies of isomer-selected and resolved chemical reactions can shed light directly on how form leads to function. In the following, we present the results of gas-phase reactions between acetylene cations (C2D2+) with two different isomers of C3H4: propyne (DC3D3) and allene (H2C3H2). Our highly controlled, trapped-ion environment allows for precise determination of reaction products and kinetics. From these results, we can infer details of the underlying reaction dynamics of C2H2+ + C3H4. Through the synergy of experimental results and high-level quantum chemical potential energy surface calculations, we are able to identify distinct reaction mechanisms for the two isomers. We find long-range charge exchange with no complex formation is favored for allene, whereas charge exchange leads to an intermediate reaction complex for propyne and thus, different products. Therefore, this reaction displays a pronounced isomer-selective bi-molecular reactive process.